LV10023B

LV10023B - Geometrical isomer of 1-substituted-1-triazolylstyrenes, and their production and use as fungicide, herbicide and/or plant growth regulant

Info

Publication number: LV10023B
Application number: LVP-92-391A
Authority: LV
Inventors: Yuji Funaki; Hirofumi Oshita; Shigeo Yamamoto; Shizuya Tanaka; Toshiro Kato
Original assignee: Sumitomo Chemical Co
Priority date: 1979-03-20
Filing date: 1992-12-22
Publication date: 1995-02-20
Also published as: BR8001617A; IL59671A; NL192791B; DK118580A; FR2460939A1; NZ193168A; DK157811B; US4554007A; IT1143014B; GB2046260A; US4749716A; YU42969B; DE3010560C2; FR2460939B1; AU536825B2; IL59671A0; NL8001658A; CH644851A5; LV10023A; CA1154449A

Description

LV 10023

GEOMETRICAL' ISOMER OF 1-SUBSTITUTED-1-TRIAZ0LYLSTYRENES, AND THEIR PRODUCTION AND USE AS FUNGICIDE, HERBICIDE AND/OR PLANT GROWTH REGULANT 1 The present inv.ention relates to one of the two geometrical isomers (a compound defined as i-A isomer in the description below) of a triazole compound represented by the formula (I),

5 wherein R^ is a hydrogen atom, a C^—Cļ, alkyl, C3—cii alķenyl or 2-propynyl group, R2 is a C-j-Cg alkyl, cyclopropyl or l-methylcyclopropyl group, R^, which may be the same or different, is a halogen atom, a C^—Cļļ alkyl, halogen-substituted C^-C^ alkyl, C^-C^ 10 alkoxy, phenoxy, phenyl, cyano or nitro group, n is an integer of 0 to 3, and the term, halogen, means chlorine, bromine and fluorine atoms, its salts, production thereof and fungicide, herbicide and/or plant growth regulator for agriculture and horticulture containing 15 said compound as an active ingredient.

Every triazole compound of the formula (I) has two geometrical isomeric forms, Z-form and E-form, , represented by the f.ormulae,

H .CH - R \ /

>C = C ^ \ ) // \

E-form Z-form 1

It is not clear at present which of the two isomeric forms the eompounds of the present invention belong to, and therefore the properties of the eompounds c.an only be expressed conditionally. These two isomers 5 can be distinguished from each~other by melting point, NMR spectrum or gas chromatography, but the difference betvreen them can be cahracterized more generally and clearly by their starting material, a triazole comp.ound of the formula (II), 0

N (II) 10 wherein Rj, R^ n are'as defined above.

The triazole compound of the formula (I) is obtained by reducing a triazole compound of the formula (II) to obtain a triazole compound of the formula (I) in LV 10023 1 which is a hydrogen atom and then etherifying the resulting compound: OR,

CH = C - G - R, CH = C - CH - R, (R-j) 3 n

N

Ί —N

Reduction (R0) _^ 3 n /N Ni]_

N (I) (R1 = H) Etherification --)

(II) (I) (Rļ! Substituents other than H) wherein R^, R£, R^ and n are as defined above.

Hereupon, one of the two geometrical isomers 5 of the triazole compound (II), of which the olefin proton appears at a higher magnetic field on the NMR spectrum in deutero chloroform, is defined as II-A isomer, and the other, of which the olefin proton appears at a lower magnetic field on the NMR spectrum 10 in deutero chloroform, is defined as II-B isomer.

Purther, the compound (I) in which R^ is a hydrogen atom, produced by reducing II-A isomer, is defined as I'-A isomer; the compound (I) in which R^ is 1 the defined substituents other than a hydrogen atom, produced by etherifying I'-A isomer, is defined as I"-A isomer; and I'-A isomer and Ī".-A isomer are defined generically as I-A isomer. The corresponding compounds 5 derived from II-B isomer in the same manner as above are defined as I’-B isomer, I"-B isomer and I-B isomer, respectively. The present invention relates to I-A isomer and Iī-A isomer which is an intermediate for I-A isomer. 10 Hitherto, there have been developed a large number of organosynthetic compounds which made a great contribution as agricultural Chemicals to the stable supply of agricultural and horticultural crops by their activity against diseases and pests doing damage to the 15 crops. It is however a fact that many problems to be improved are also stili present. Such problems are sometimes solved, for example, by the development of new and more desirable pesticides, or it may be considered that they are also solved by investigating the conven-20 tional pesticides to establish a proper form of the application of agricultural Chemicals.

There are not a few organo-synthetic compounds having a possibility that they are also present in the form of geometrical or optical isomers. In fact, there 25 are many cases in which pesticides containing these isomers are in practical use as agricultural Chemicals. ,It is well known not only in agricultural Chemicals but also in many other fields that, with many of active 5 LV 10023 1 ingredients having the isomeric forms, there is observed a difference i'n biological activity between the isomers. Recently, theproblem of environmental’pollution becomes very serious in the field of agriculture and horticul-5 tūre, and it is important to lighten this problem by using one of a pair of isomers which is stronger in activity. Also, this may be considered as bringing about a more economical effect in the production of the compound as well as in the practical application as 10 agricultural Chemicals. From this standpoint, therefore, it may be considered as contributing to this field to provide the isomer having a stronger activity.

From this viewpoint, the inventors made a further study on the compounds alreaay found by the 15 inventors [Publishad Ujņexamined Japanese Patent Application No. 130661/1978 ^ ReJLgian Patent No. 870243 (Published Unexamined Japanese Patent Application No, 41875/1979)]·. As a result, it was found that the present compounds defined as I-A isomer, 20 one of the two geometrical isomers of a triazole compound represented by the formula (I), have a higher fungicidal. activity on a wider range of plant pathogens as well as a higher herbicidal effect and a higher plant growth regulating action than the compounds defined as I-B 25 isomer, in other words, they have excellent properties as agricultural Chemicals. The inventors thus attained to the present invention.

There are many other well-known triazole - 6 - 1 compounds disclosed in British Patent No. 1364619,

Belgian Patent No. 845433, West German Patent Nos. 2610022, 2654890 and 2734426, and U.S. Patent No. 4086351. But, the characterlstic of the present invention is that the 5 following new Information was found: One of the two geometrical isomers of the triazole compound (I) characterized by having both of (1) a double bond (benzylidene group) and (2) a hydroxy group or its ethers in its structure, , 1 or:

10 has far superior properties as agricultural Chemicals as compared with the other geometrical isomer. In this point, the present compounds have a different struc-tural characteristic from that of the foregoing well-known compounds, and besides they have far superior 15 properties as compared with the well-known compounds. Consequently, the originality of the present invention is such a one as to be never imaginable from the prior art.

As diseases on which the compounds of the 20 present invention (I-A isomer) can exert an excellent protective activity, there may be given rice blast (Pyricularia oryzae), sheath blight of rice (Pellicularia 7 LV 10023 1 sasakii), canker of apple (Valsa mali), blossom blight of apple (Sclerotinia mali), powdery mildevr of apple (Podosphaera leucotricha), apple scab (Venturia Inaegualis), fruit spot of apple (Mycosphaerella pomi), alternaria 5 leaf spot of apple (Alternaria mali), black spot of pear..·, (Alternarla kikuchiana), powdery mildew of pear (Phyllactinia pyrl), rust of pear (Gymnosporangium haraeanum), scab of pear (Venturia nashicola), melanose of citrus (Diaporthe citri)3 citrus scab (Elslnoe 10 fawcettl), common green mold of citrus fruit (Penicillium digitatum), blue mold of orange (Penicillium italicum), brown rot of peach (Sclerotinia cinerea), anthracnose of grape (Elsinoe ampelina), ripe rot of grape (Glomerella cingulata), gray mold of grape (Botrytis cinerea), 15 powdery mildevr of grape (Uncinula necator), rust of grape (Phakopsora ampelopsidis), crown rust of oats (Puccinia coronata), powdery mildevr of barley (Erysiphe graminis), leaf blotch of barley (Rhynchosporium secalis), stripe of barley (Helminthosporium gramineum), loose 20 smut of barley (Ustilago nuda), covered smut of barley (Ustilago hordei), typhula snovr blight of barley (Typhula incarnata), stem rust of barley (Puccinia graminis), leaf rust of wheat (Puccinia recondita), loose smut of wheat (Ustilago tritici), bunt of wheat 25 (Tilletia caries), speckled leaf blotch of wheat (Septoria tritici), glume blotch of wheat (Septoria nodorum), yellow rust of wheat (Puccinia striiformis), 'stem rust of wheat (Puccinia graminis), powdery mildevr - 8 - 1 of wheat (Ervsiphe graminis), powdery mildevrof cucumber (Sphaerotheca fuliginea)v gray mold of cucumber (Botrytis cinerea), gummy stem blight of cucumber'(Mycosphaerella melonis), sclerotinia rot of cucumber (Sclerotinia 5 sclerotiorum), anthracnose of cucumber (Colletotrichum lagenarium), leaf mold of tomato (Cladosporium fulvum), powdery mildew of tomato (Erysiphe cichoracearum), early blight of tomato (Alternaria solani), gray mold of egg-plant (Botrytis cinerea), verticillium wilt of eggplant 10 (Verticillium albo-atrum), powdery mildew of eggplant (Erysiphe cichoracearum), powdery mildew of pimento (Leveillula taurica), gray mold of strawberry (Botrytis cinerea), powdery mildew of strawberry (Sphaerotheca humuli), brown spot of tobaccp (Alternaria longipes), 15 powdery mildew of tobacco (Erysiohe cichoracearum)a cercospora leaf spot of beet (Cercospora beticola), leaf spot of peanut (Cercospora personata), brown leaf spot of peanut (Cercospora arachidicola) and the like.

By further study on the antimicrobial activity 20 of the present compounds, I-A isomer, it became clear that the present compounds exhibit also an antimicrobial activity against Trichophyton rubrum. Thus, it was found that there is a possibility of the present compounds being usable as an antimycotic for medical 25 piirposes.

Further} the compounds of the present invention, I-A isomer, can also be used as a plant growth regulator, acting to control the growth of useful plants. For 9 LV 10023 1 example, they canbe used for preventing the spindly growth of rice, wheat, turf, trees for hedge and fruit trees and for dwarfing horticultural pl'ants such as potted chrysanthemum. 5 In the cultivation of rice and wheat, lodging of rice and wheat caused by the application of more fertilizer than required or strong wind becomes often serious. But the application of the present compounds at a proper time is effective for controlling 10 the height of rice and wheat and preventing lodging.

In the cultivation of potted chrysanthemum, the application of the present compounds is useful to elevate the commercial value of the chrysanthemum because they can shorten the height of the_stem with no adverse 15 effect on the flower.

The compounds of the present I-A isomer, invention have a strong herbicidal activity against . grassy field weeds such as barnyard grass (Echinochloa crus-galli), large crabgrass (Digitaria sanguinalis) 20 and green foxtail (Setaria viridis); broad-leaved field weeds such as Umbrella plant (Cyperus difformis L.), redroot pigweed (Amaranthus retroflexus), common lambsquarter (Chenoooaium album), common purslane (Portulaca oleracea) and chickweed (Stellaria media); 25 and annual weeds and perennial weeds in paddy field such as barnyard grass (Echinochloa crus-galli), pickerel weed (Monochoria vlaginalis), toothcup (Rotaļa indica Koehne), Dopatrium junceum, Bulrush sp. (Scirpus 10 1 juncoides var. Hotarui Ohwi) and slender špikerush (Eleocharis acicularis).

When the compounds of the present invention are applied to fields, they are also very superior in the 5; following points: They have a strong herbicidal activity against main weedš in fields; they show the activity by either of soil treatment before the germination of weeds or foliage treatment at the beginning of growth; and besides they can be applied safely without doing damage 10 to main crops (e.g. rice, soybean, cotton, corn, peanut, sunflower, beet) as well as vegetables (e.g. lettuce, radish, tomato). When the compounds of the present invention are applied to paddy fields, they show also a strong herbicidal activity against main weeas by either 15 of pre-emergence treatment or foliage treatment at the beginning of growth, and besides they have a high safety to rice plants.

Further, the compounds of the present invention are very useful as herbicides not only for paddy rice 20 but also for various crops, vegetables, orchards, turfs, pasture lands, tea gardens, mulberry farms, rubber farms, forest lands and non-cultivation lands.

Further, it became clēar that the compounds of the present invention have a high safety to mammals 25 and fishes, and besides.that they can practically be used .. without doing damage to useful crops in agriculture.

The triazole compounds II-A, an intermediate for producing the present compounds I-A, have also a 11 LV 10023 1 fungicidal activity against various pathogens doing damage to agriculture as well as a herbicidal and plant growth regulating action. It is also a’ fact, howeverļ that the present compounds I-A have a far stronger 5 activity against a wider range of plant pathogens as well ās a far stronger herbicidal and plant growth regulating action than the compounds II-A.

More specific methods for producing the present compounds will be given below:

10 Method A: Reduction of the triazole comDOund II 0 (R3}n Iī-A isomer

Ϋ yCH = C - C - R2 •N

wherein R2, R^ and n are as defined above.

The Ī'-A isomer is producea by reducing the II-A isomer in a suitable solvent with a mētai hydride complex (e.g. lithium aluminum hydride, sodium borohydride) 15 or aluminum alkoxide (e.g. aluminum isopropoxide).

The II-A isomer to be reduced can be obtained in a pure form, for example, by applying fractional crystal-lization or column chromatography to the mixture of the geometrical isomers of a triazole compound (II) produced 20 according to the following reaction equation. The II-A isomer can also be obtained in a good yield, for examplei 12 1. by irradiating the mixture with ultraviolet rays to carry out photoisomerization. More detailed explanation will be given hereinafter with reference to Methods C and D. 0

(II) 5 wherein R2J R^ and n are as defined above.

The solvent used in the reduction with a mētai hydride complex includes for example ethers (e.g. diethyl ether, tetrahydrofuran) and alcohols (e.g. methanolj ethanol, isopropanol). When sodium borohydride 10 1s used as the mētai hydride complex3 the reaction is achieved by mixing 1 mole of the II-A isomer and 0.25 to 2 moles of sodium borohydride in a solvent. The reaction temperature is preferably within a range of 0°C to room temperature. The solvent used includes 15 for example ethers (e.g. diethyl ether, tetrahydrofuran) 13 - LV 10023 1 and alcohols (e.g. methanol, ethanol, isopropanol).

When lithium aluminum hydride is used as the mētai hydride complex, the reaction 1s achieved by dissolving lithium aluminum hydride of 0.25 to 0.8 time by mole 5 based on the II-A isomer in a solvent and adding the resulting solution to a solution of the isomer in the same solvent. The reaction temperature is preferably within a range of -60°C to 70°C. The solvent used includes ethers (e.g. diethyl ether, tetrahydrofuran). 10 After completion of the reaction, water or an aqueous dilute acid is added to the reaction solution, and after neutralization with an alkali if necessary, the deposited crystals are collected by filtration or extracted with an organic solvent sparingly soluble in 15 water. The subsequent treatment is carried oūt by the common methods.

When aluminum isopropoxide is used as reducing aģent, it is preferred to use such solvents as alcohols (e.g. isopropanol) or aromatic hydrocarbons 20 (e.g. benzene). It is a common practice to allow 1 mole of the II-A isomer to react with 1 to 2 moles of aluminum isopropoxide at a temperature betvreen room temperature and 100°C. The resulting aluminum compouna is decomposed with a dilute sulfuric acid or an aqueous 25 s'odium hydroxide solution, followed by extraction with an organic solvent sparingly soluble in water. The subsequent treatment is carried out by the common methods.

The salts of the I’-A isomer refer to those 14 - 1 obtained with plant-physiologically acceptable acids such as hydrohalogenic acid (e.g. hydrobromic acid, hydrochloric acid, hydroiodic acid), carboxylic acids (e.g. acetic acid, trichloroacetic acid, maleic acid, 5 succinic acid), sulfonic acids (e.g. p-toluenesulfonic acid, methanesulfonic acid), nitric acid, sulfuric acid and phosphoric acid. If necessary, these salts are produced by the conventional methods.

Method B: Etherification of I'-A isomer

ORi 1 CH " r2 Etherification \ -7

CH = C - CH - R. OR,

/Ns N ļ ϋ-N I'-A isomer (R^ = H) I"-A isomer (R.: Substituents other than H) 10 wherein R^, R2, R^ and n are as defined a’oove.

The present compounds, I"-A isomer, are obtained by reacting I'-A isomer with a reactive C^-Cj, alkyl, C^-C^ alkenyl or 2-propynyl derivative in a suitable solvent in the presence of a base. The reactive 15 derivative includes for example alkyl-, alkenyl- or alkynyl-halides (e.g. methyl iodide, allyl bromide, propargyl bromide), sulfate compounds (e.g. dimethyl sulfate, diethyl sulfate) -and sulfonate compounds (e.g. p-toluenesulfonate, naphthalenesulfonate). 20 The solvent includes for example general inert organic - 15 - LV 10023 1 solvents such as diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene and dimethylformamide. This reaction may be carried out in the presence of water using a phase transfer catalyst known as a reaction 5 accelerator (e.g. triethylbenzylammonium chloride, trimethylbenzylairanonium bromide). The base includes for example 'suitable strong bases (e.g. alkali mētai hydrides such as sodium hydride, alkali mētai amides such as sodium amide), carbonates (e.g. sodium 10 carbonate, potassium carbonate) and alkali mētai hydroxides (e.g. potassium hydroxide, sodium hydroxide).

This reaction is achieved by mixing I'-A isomer, a reactive C^-C^ alkyl, -C^ alkenyl or 2-propynyl derivative and a base, preferably in an 15 eauimolar ratio in a suitable solvent. The reaction is carried out within a range of 0° to 100°C, preferably 20° to 60°C. Sometimes, it is favorable to firstly react I’-A isomer with a suitable strong base (e.g. alkali mētai hydrides, alkali mētai amides) in an inert solvent 20 and then to react the resulting alkali mētai salt with a reactive alkyl, C^-C^ alkenyl or 2-propynyl derivative.

In some cases, the following way is desirable to isolate the present compounds I"-A: The reaction 25 mixture is freed from the solvent by evaporation, water and an organic solvent sparingly soluble in water are added to the residue, the organic layer after extraction is separated and then purification is carried 16 - 1 out by the usual methods.

The salts of the I"-A isomer refer to those obtained with physiologically acceptable acids such as hydrohalogenic acid (e.g. hydrobromic acid, hydrochloric 5 acid, hydroiodic acid), carboxylic acids (e.g. acetic acid, trichloroacetic acid, raaleic acid, succinic acid), sulfonic acids (e.g. p-toluenesulfonic acid, methane-sulfonic acid), nitric acid, sulfuric acid and phosphoric acid. If necessary, these salts are produced by the 10 conventional .methods.

The present invention will be illustrated in more detail with reference'to the following examples. Unless otherwise stated, NMR spectrum in the examples is indicated by 6 values with deutero chlorofcrm as a solvent 15 and tetramethylsilane as an internai Standard.

Example 1

Synthesis of the I'-A isomer of l-(4~chlorophenyl)-4, 4-dimethyl-2- (1,2,4-triazole-l-yl) -l-pentene-3-ol (Compound No. 1) by MethodA 20 The II-A isomer (2.9 gs 0.01 mole; m.p. 108° - 109°C) of l-(4-chlorophenyl)-4,4-dimethyl-2-(l,2,4-triazole-l-yl)-l-pentene-3-one (Compound No. 1') was dissolved in methanol (50 ml). Sodium borohydride (0.38 g, 0.01 mole) was added thereto while keeping 25 the temperature of the reaction solution at 20°C or less with ice-cooling. The reaction mixture was ķept āt 20°C for 3 hours, and then decomposed with addition 17 LV 10023 1 of water (100 ml) and acetlc acid (1 ml). The orgānic layer was extracted with ethyl acetate (100 ml), and the extract was washed with a 5 % aqueous sodium hydrogen carbonate solution (50 ml) and dried over anhydrous 5 sodium sulfate. The solvent was then removed under reduced pressure, and the residue obtained was recrystallized from isopropanol to obtain 2.0 g (yield 69 %) of the I’-A isomer having a melting point of 153° - 155°C. The elementary analysis and NMR spectrum 10 of the compound are shown below.

Elementary analysis: c($) E(%) N( #) Cl(^) Calculated (as C15Hl8N3OCl) 61.74 6.23 14.40 12.15 Found 61.82 6.33 14.38 12.15 NMR spectrum: 8.52 (ĪH, s, triazole proton) 7.98 (1Hj s, triazole proton) 15 7.30 (4H, s, phenyl proton) 6.9i (1H3 s, olefin proton) 4.56 (2H, broad singlet, hydroxyl proton and methine proton carrying an OH group) 0.66 (9H, s, butyl proton) 18 - 1 Comparative Example 1

Synthesis of the I'-B isomer of l-(4-chlorophenyl)-4,4-dimethyl-2-(l,2,4-triazole-l-yl)-Ī-pentene~3-ol (Compound No. 1) 5 The II-B isomer (2.9 gs 0.01 mole; m.p. 78° - 79°C) of l-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-l-yl)-l-pentene-3-one (Compound No. 1’) was dissolved in methanol (50 ml). The isomer was allowed to react with sodium borohydride and then treated in the 10 same manner as in Example 1. The reāidue obtained was recrystallized from a 1:10 mixture of carbon tetrachloride and n-hexane to obtain 2.2 g (yield 76 %) of the I’-B isomer (m.p. 116°-117°C) of Compound No. 1. The elementary analysis and NMR spectrum of the compound 15 are shown below.

Elementary analysis: c(%) H(Sf) N(ī) Cl(%) Calculated (as C15Hl8N3OCl) 61. 6.23 1^.40 12.15 Found 61.80 6.25 14.52 12.09 NMR spectrum: 7-92 (s, triazole proton) 7.77 (1H, s, triazole proton) 20 7.05 (2H, d, phenyl proton, J = 9Hz) 6.58 (2H, d, phenyl proton, J = 9Hz) 6.66 (1H, s, olefin proton) 4.28 (1H, d, methine proton carrying an OH group, J = 6Hz) LV 10023 1 3-21 (1H, d, hydroxyl proton, J = 6Hz) 0.80 (9HS s, butyl proton)

Example 2

Synthesls of the I’-A isomer of 3-(if-chlorophenyl)-5 l-(l-methylcyclopropy1)-2-(1,2,4-triazole-l-yl)-2-propene-l-ol (Compound No. 30) by Method A

The I'-A isomer (2.9 g3 0.01 mole; m.p. 89° -92°C) of 3“(^-chlorophenyl)-l-(l-methylcyclopropyl)-2-( 1,2, ii-triazole-l-yl)-2-propene-l-one (Compound No. 10 29') characterized by the NMR spectrum described below was dissolved in methanol (50 ml). Sodium boron hydride (0.38 g, 0.01 mole) was added thereto while keeping the reaction temperature at 20°C-er less with ice-cooling. The reaction solution was ķept at 20°C for 3 hours, and 15 then decomposed with addition of water (100 ml) and acetic acid (2 ml), The organic layer was extracted with chloroform (100 ml), and the extract was washed with a 5 % aaueous sodium hydrogen carbonate solution (50 ml) and dried over anhydrous magnesium sulfate. 20 The solvent was then removed under reduced pressure, and the residue obtained vras crystallized from a carbon tetrachloride/n-hexane (1:1) mixture (5 ml) to obtain 2 Λ g (yield 85 %) of the entitled compound.

The NMR spectrum of the starting material, 25 II-A isomer of 3-(/i-chlorophenyl)-l-(l-methylcyclo-propyl)-2-(l,2,i»-triazole-l-yl)-2-propene-l-one, is as follovrs: 20 1 8.28 (1Η, s, triazole proton) 8.07 (1H, s, triazole proton) 7.32 (MH, s, phenyl proton) 7.19 (1H, s, olefin proton) 5 1Λ5 - 1.15 (2H, ra, methylene proton of cyclopropyl group) 1.25 (3H, s, methyl proton) 0.99 - 0.75 (2Hj m, methylene proton of cyclopropyl group) . 10 Comparative Ēxample 2

Synthesis of the I'-B isomer of 3-(**-chlorophenyl)-l-(l-methylcyclopropy1)-2-(1,2,4-triazole-l-yl)-2-propene-l-ol (Compound No. ~30)

The I'-B isomer (2 g, 0.007 mole; m.p. 7^° -15 75°C) of 3-(4-chlorophenyl)-l-(l-methylcyclopropyl)- 2-(l,2,il-triazole-l-yl)-2-propene-l-one (Compound No. 29 *) characterized by the NMR spectrum described below was reduced, in the same manner as in Example 2, with sodium borohydride (0.27 g, 0.007 mole) in methanol 20 (50 ml). Thus, 1.7 g (yield 85 %) of the entitled compound was obtained.

The NMR spectrum of the starting material, II-B isomer of 3-(^-chlorophenyl)-l-(l-methylcyclopropyl) 2-(l,234-triazole-l-yl)-2-propene-l-one, is as follows: 25 8.12 (1H, Sj triazole proton) 8.03 (1H, s, triazole proton) 7.55 (1H, s, olefin proton) LV 10023 1 7.21 (2H, d, phenyl proton, J = 8Hz) 6.8l (2H, d, phenyl proton, J = 8Hz) 1.50 - 1.25 (2H, m, methylene proton of cyclo-propyl group) 5 1.28 (3H, s, methyl proton) 0.90 - 0.65 (2H, m, methylene proton of cyclo-propyl group)

Example 3

Synthesis of the I'-A isomer of l-(4-chlorophenyl)-10 4, iJ-dimethyl-3-methoxy-2-(l, 2,4-triazole-l-yl)-l-

pentene (Compound No. 35) by Method B

The I'-A isomer (2 g) of l-p-chlorophenyl-4,4-dimethy 1-2-(1,2, ii-triazole-l-yl)-l-pentene-3-ol (Compound No. 1) was dissolved in dimethylformamide 15 (20 cc), and 65 % oily sodium hydride (0.26 g) was adaed thereto. After stirring for 1 hour at room temperature, the reaction mixture was cooled to 10°C, and methyl iodide (1 g) was added. After standing at room temperature for 20 hours, the solvent was removed 20 under reduced pressure, and the residue obtained was extracted with addition of ice water (100 g) and chloroform (100 cc). The organic layer was dried over anhydrous magnesium siilfate, and the solvent was removed under reduced pressure. The oily crude product obtained 25 was purified by column chromatography on silica gel (acetone:n-hexane = 1:10) and further recrystallized from a carbon tetrachloride/n-hexane (1:2) mixture to 22 1 obtain 1.6 g of the entitled compound (m.p. 63° - 66°C). Comparative Example 3

Synthesls of the I"-B isomer of l-p-chlorophenyl-4,4-dimethyl-3-methoxy-2-(1,2,4-triazole-l-yl)-l-5 pentene (Compound No. 35)

The I'-B isomer (.2 g) of l-(4-chlorophenyl)-4,4-dimethy1-2-(1,2,4-triazole-l-y1)-pentene-3-ol (Compound No. 1) vras dissolved in dimethylformamide (20 cc), and 65 % sodium hydride (0.26 g) was added 10 thereto. After stirring at room temperature for 1 hour, the reaction mixture was cooled to 10°C, and methyl iodide (1 g) vras added. The reaction mixture vras ķept at 10°C for 1 hour and then allovred to stand at room temperature for 16 hours. Dimethylformamide vras 15 removed under reduced pressure, and the residue vras extracted vrith addition of ice vrater (100 g) and chloroform (100 cc). The organic layer vras dried over anhydrous magnesium sulfate, and the solvent vras removed under reduced pressure. The resulting crude product vras 20 purified by column chromatography on silica gel (acetone:n-hexane = 1:10) to obtain 1.0 g of the entitled compound as an oily product. 27

Refractive index n^ 1.5435 Elementary analysis: c(%) M) N(%) Cl(Jt) Found 62.90 6.60 13.77 11.50 Calculated (as Cl6H20N3C10) 62.84 6.59 13.74 11.59 23 - LV 10023 1 The present compounds (I-A isomer) obtained by

Methods A and B are shown in Table 1. Por comparison, the data on I-B isomer was shown together. Unless otherwise stated, NMR spectrum in the table is indicated 5 in δ values with CDCl^ as a solvent and tetramethyl-silane as an internai Standard. The I'-A isomer and I"-A isomer are generically called I-A isomers and the I'-B isomer and I"-B isomer are also generically called I-B isomer. This generic indication is also used in 10 the tēst examples described below. 2k I Table H 3 Ph 40 υ ω a co cd ε 2 Η CM cd I rH cd a 0—0

I

I c on Cd tu H o N CŪ •H u ε» 40 o Ph a r~1 40 a c O Cti •rl 40 CO CO C •C O a o a o Ό C •H 2 40 P-, ω ωε ε ο Η Ο ω α3 co bO ο ·Η οη cd

Cd

CM

Cd Ό c 3 · o o as ε

O O oo a\ c- a CM tn oo o o LTv LA rH I on la a 6 < I Η

Cr~ t— CM CTi o o c~- rH rH I vo rH i—! a ο I -=τ on on td o %__ o te tr- o\ un vo OJ o

CM OO σ\ o vo c— oo oo

A in =r oo o o CT\ I co •=r aε < I Η Λ o σ\ i>- o o vo =r I—I aε PQ I Η Ο I Ή Ό

CM

CM tn LTt oo o o σν i vo •=X I—I a < I Η co σν o-

o o co CM i—1 I t- CM aε CP 1 Η Ρη cq ι on CM oo on σν oo c~-

Cont1 d

I o o =r o CM I on o CM a ε

0 o LA 00 1 CM CO aε Η CQ I Η -rr 25 LV 10023

Table 1 (Cont'd)

Cont1 d 26

Table 1 (Cont'd) H in rH -=r Lf\ LO o -=T LO 0J σ\ m m CT\ co (—1 t- o co CT\ o\ o σ\ VO cr\ oo OJ <0\ cr\ co oo 0- t>- co 0- 0- 0- 0- .c— oo O- t— r\ r\ Λ Λ Λ Λ #\ c\ *> ό OJ O co VO O VO σ\ LTi rH o LPv o σν c— σ\ o tn σ'» cn rH irv ο σν in O σν o *ξγ oo co oo t·- co oo co co co c·- co 00 00 CO co o o O O o o o ο o o o O o o o 0 o 0 0 0 0 0 0 0 0 0 0 o 0 0 o o rH OO ΟΊ «=T · LTV o c— oo LO LO c«- rH VO c·^ VO o σ\ ι—I in ov in OJ ΟΊ 0J VO rH rH rH rH rH rH Η rH rH rH rH 1—1 rH 1—1 co c\ co OJ C\J C\J rH rH I 00 1 co 1 tn 1 c— -=r CO vo o LTV c- VO o cr\ rH LO co LT\ OJ σν OJ VO rH rH rH rH i—l rH rH rH rH rH rH rH rH rH a a a a a a a a a a a a a a a ε ε ε ε ε ε ε ε ε ε ε ε ε . ε ε < | CQ I < 03 < 03 < CQ < 03 < 03 < 03 < H H Η H H H H M 1 H I H H H H H H >5 I—1 ><! >3 O c oo C φ oo 0J 0 rH r- O 2 o JO o | a O o K o a OJ -Γ -=r -=T —«4 m /-S oo t-U O — — — — — o ir\ VO c— co ov o (—I 0J rH rH ι—1

Cont' d 27 LV 10023

Table 1 (Cont'd)

Cont' d 28

Table 1 (Cont’d)

CM •=t CM CM CM C7\ CO oo CO o 00 O oo O OC O OO o CO o OC o CT\ • • • • • • • • ΟΛ • 4 • oo c— CO 0- OO c— oo c~- • c— oo 0- 0- Λ *> r> Λ Λ *n 1 CM #\ Λ r\ OJ c- CM CO σ\ o oo m OC Lf\ SK CM CM a\ ĻO o CO o ΙΓν 1—1 C-- o C**--=y λ -=r LH o · ♦ • • • • • • . • . . £ • • • OO oo CO 00 CO CO CO oo CO CO v— CO CO CO o o Ο o o o o o o 0 o 0 0 0 0 o 0 o 0 CM CM o ιη t- LT\ oc CO o cr\ =T rH o • o LH rH oo CTC CO o oo 1—1 i—1 CO oo rH O rH rH 1—1 rH t- 1 1 LA CM 1 in 1 1 1 1 1 H o • C— H CO 4 C— CO CM C— 1 oo =T 1—1 rH CM o rH rH oo oc CO 0- 00 rH rH Η 1 rH rH rH i—I rH CO CO LH o, α p CM P p P cmP p p p P P E £ E c fcī E c E E E E £ < I CQ I < I CQ < CQ < m < CQ < CQ H H H H H H 1 H H 1 H H H H CM oo o E 2 o , 1 o LPi oo 1 i—1 Ph i—1 o z z o o Ph l -=r oo CM oo oo rs CM CM oo ro oo X X X X K CO o — -o o o o CH V/ H \ o o 1 o 1 E r = - r oo j=r LTV CO 0- CO i—l t—1 i—1 1—1 1—I 1—I

Cont' d 29 LV 10023

Table 1 (Cont'd) χ-\ ε ε A α Α Α /-N /-N X κ /-S N N •ΞΓ -=Γ Ν Ν X X w κ ίϋ vo vo rH rH VO νο ο ο II II ♦ • II II ο ο *“3 1 I •"D a Λ α Α Ό T3 ο ο Ό Ό VO VO • « Α Α LA rH Ο ο Χ'-' X^ <=τ LA ι—I CO Ο ι—1 m oo ΓΟ Ν οο t3 ο- 00 ο- CO 0- οο * * Α Α '-'Χ « • • • * • i—l t—I ✓~s ο Ο ο ο ο ο ε ε Η ΚΩ ονο ο ο α α • II • II κ « Η 1—1 ι—! rH •“3 1-3 α Λ Λ /*S Α ια ια ε ό ε ·σ VO νο • • α α Α Α ο ο Ε κ X X Η ΟΟ ι—ί ΟΠ 1 I V_/ \_/ ο LA c\i OJ C— 1—1 ι—1 ια ο- ιησ\ ι—! 1—1 .Η Ο <Η ο Ο» — οι Η-ι /-"S ✓—Ν 03 Ν ο- 0) Ν X κ X Ν. Α /-Ν B ο- ε CT\ Ν ε CO ΙΑ ε ε X II II II II o ΙΑ ΚΩ Ο ο ο la *-3 VO >“D LΑ -=τ 1—ί • • II « • • -=T Λ οη Α _τ Α Α -=Γ -=Γ B Ό Ό hD Ό Ό 1 1 1 V—· ι I Α i—I la -=Τ ο \Ω Ό ο VO ΓΟ ΓΑ ο ο i—f CT\ ι—1 ο 00 Ό ο οο -=Γ 00 -=Γ • • • • • • • • • • « IA -=r -=Γ ·=τ =τ ΙΑ -=Γ -=Χ =Γ *=Γ ΟΟ CM ο LA CO ΟΟ O ο- VO -=Γ ιΗ LA Ο CO • ΙΑ ο- νο νο ov c- OV CO Ο 0- ι—1 0- Ο οο VO VO VO VD 0- ΚΩ ΚΩ C— VO Η ιΗ 0:Κ O-.f- ΓΟ^-ν σκ'-' • ε Β C----' ΚΩ w

Cont ’ d 30

Table 1 (Cont1d)

i—1 VO rH VO LT\ CO σ\ LA .=r vo CT\ CM LA o o 00 O c— oo OV CT\ o\ σν o CO co c— co C- CO O- o- t>- c-- t*- co c- A A * A A A A A A A Λ A A LA co LA vo CM CTV VO CO 0\ -=r o H o CO la ov LA o C~- o\ LO o •=r o -=r 1-1 LA o co t>- OO co CO t>- CO co oo oo co co CO 00 o O o o o o o o 0 0 0 0 0 0 0 0 o o co vo LA CO CM oo CM -=T OJ co o O o t>- vo CO iH t“- co σ\ -=T co CM rH ir\ o in i—! «ΞΓ CM co i—I rH rH rH • 0 la 1 1 1 LA 1 LA LA 1 1 1 1 vo c— • o -=r • . o • • CM Γ—1 vo σν c— co rH C-- vo co rH tr- i—1 rH ST co CM o 1—I 1-I rH rH i—1 rH 1—1 vo vo =T -=r a a CMD a a a CMD a CMD CMD a a a a £ Ē C ε ε ε c . ε C c ε ε £ ε < 1 CQ < ra < CQ < CQ < CQ < Cū < CQ H H H H H H H H H H H H M H CM i—! f-N co o co s -< o oo o CM Ό O i—l rH 3 o rH o o co o o o o A [ co —4 CM —J Γ co CO co 3 M CO tc co O ✓-n o co co co co LA co K X tc co 3 /*~N K O o O CM o V_>· CM +r-i V__' CM o •-H o O o K o •--- o 1 · σ\ o rH CM co LA r~ λ CM CM CM CM CM CM

Cont' d 31 LV 10023

Table 1 (Cont'd)

Cont' d 32

o o 00 c— in co o o lh Ln aε oo c— oo o co •=T sf:

οο CO

ο VO οο CO Ο νο ο

CO CM ο ο

CO ιη ιη οο

ο ο CO

νο CO

ιΗ ο CO ο C— >- CO ον ο LTV οο CO ο οο νο ir co νο ον

Cont * d CM LH =r UO i—1 OO CM Q c O o CM uo i—I I H LH r-1 aε ο ο ΟΝ ΜΟ ιΗ I 00 νο I—I & CT\ οο VO ιη

CMO C ο ο LT\ ιΗ γΗ I ir >Η aε ο ο 0- CM I—1 I ιη CM I—I aε ο ο ο οο γΗ 1 ο— CM ι—1 aε ο ο LH ο Η I οο ο aε ο ο CM CM ι—I I ο CM I—1 aε ο ο σν I—1 ι—I I 00 ιΗ ιΗ aε ο ο ο iT ι—I 1 σν οο I—I aε

Table 1 (Cont'd) < I Η ω I Η < I Η pa < I Η pa ι Η pa I Η < I Η pa I Η < [ Η pa I Η ι—I ο ο I •γΗ

CM ι—! ο I ir

CM I—I ο I •Η Ό I ir Α CM οο ο οο ρρ ο CM ΡΡ ο οο m X ο ο οο X ο CM X ο CM X ο

οο ΡΡ ο \ΡΡ/ ο I οο ΡΡ ο CM ΡΡ ο

CM Τ' Ο CM \ΡΡ ΟΟ | Ο μ- / Ο—ο I νο ΓΜ C— ΓΜ ΟΟ ΟΜ

σν CM Ο ΟΟ ΟΟ 33 LV 10023

Table 1 (Cont'd)

Cont ’ d - 31» -

Table 1 (Cont'd) I—1 CM LA rH CM co o LA LA o σ\ O co OV 00 o C\ co c— OO c— C- C-- co t- C- Λ «\ ** 1 1 «\ i—1 in «r -=r C7\ o\ vo CO O la rH LA o -=X o LA LA VO co co CO 00 co co CO OO co o o O o o o 0 o o o 0 o O c- LA .=r co t— rH 0 LA CM o o o CM CM 00 CM CM vo CO LA 00 σν rH rH rH rH r—1 MD •ΞΓ .=r co co I 1 1 1 1 1 LA LA LA LA LA co o rH LA o 1 • • • • O CM OJ co CM CM co rH rH 1—1 rH rH rH rH rH rH vo vo c— vo α α & o. a & a CMQ CMQ CMQ CM Q E E E E B B E C C c c < I pa < I pa < ra < CQ < X < H H H H H H H H H f—1 H U — 1—1 PP X o π - —u -=T 1 co CM X co o CM X \ts z o s CO 1 O X / o o—o 1 co aa o co co co X “ r X X CM o o X CM o X • a 1 CM m =x LA VO c--- CO CO co CO co co

Cont1 d 35 LV 10023

Table 1 (Cont'd)

Cont * d 36 co on OJ un co

-=r NO

LA

NO CMQ C

<I ont— c— la co

Oo co t— ia co CO ο co

00 NO

CO NO ONt*-'

LfN LfN 00

CO ON H in oo

CO ON

O UN

CO

-=T ON

LfN OO

CM CO

NO ON

Cont ‘ d

co LA CUQ c

coo ir\ LA no ojd c CO sts oo coc—I OJο-α ε la ΟΝ un cn CM Qc

O OJ OJ LfN LA CM Qc

CM co co LfN

NO CMO C

in LfN co LA

LfN CMO C

ON iH NO LfN NO CM O c

CO CO NO UN

NO CM Q C

O CM LA UN

NO CM Q C

Table 1 (Cont'd)

caIM

<IH

PQI H <ι Η

<IH

< I H

CQ I H

< I H

r-1oI =T

(¾ I

X

G X I

CM O X I CO COXo o OJ •“1—· o X o __CM ►J-. o CO XoO II Xo CM Xo CO X Ο CO Xo OJ Xo OJ Xo OJ Xo II Xo CM Xo CO X o co X o CM X o II X o CM X o co Xo co co cr\ co ο^r

CM co -=r

UN -=T

NO LV 10023

Table 1 (Cont'd)

Cont1 d 38 •=r σ\ OJ ia co o LA LA la

co cmQC o o co OJ la co OV σ\

i—I KO co KO cr\ OJ in co t>- o co

co KO co o o co

OJ MD

CO o LT\ ia

KO OJ Q C o lo co ιa

•=r CM QC oc^- LA la

CM OJ QC

o co co LA OJ OJ Qc

LA CO LA LA LA CMQc

KO =r LA

t— CMQC

LA LA IA OJ Qc O o co

o KO 00

ooOJ KO rHI i—I KO iHCL E -α-αο

CMO

CO

O o rH CM i—II o OJ

CL E o o co

OJ LA

CO

O 0 KO 00I LA CO

aE coc- coo co

o oc— PO ι—II KO cn rHa E

Cont' d

Table 1 (Cont'd)

«IH

<ι H

<IH

CQIH

<IH

<I H

CQI H

<I H

CQI H

coXO

rHOI

\X / oI co Xo

I—(oI•HXI co Λ CM

CO

o01 OJ

I—ioI•HXI -=T OJ

rHoI •H X I LA CO

LA X OJoI co co X o '—' o X o III o CM X o co X o co =r CM X o X ϋ OJ X o OJ X o II X o CM X o

CO X o OJ X o II X o OJ X o a\ =r

o IA

LA

CM LA

CO LA

•=r LA - 39 - LV 10023

Cont ’ d ir\ o-o in c- m c- LT\ C-- \Ω ir\ c·— co

Hco o c-

iH CO

Table 1 (Cont'd) N ĪCvo II '“D Λ n N II h) Λ Ό

vo II •"D TS

o OJ

o i—I

o CM 0- o\co coo

LTV

O PO I—I c—

\o OJ co [— ir\co oco LT\ i—I 0“ i i—I in* co*~ 0-' LT\m o =r oco c- coco vo vo CM*

\D CM CTi

MO

cr> MD vo - ko -

Table 1 (Cont'd) OJ tn O CM o o\ O O • • « « OD c~- CO 00 *) Λ i—1 -=T. rH vo o vo o * * • • CO CO CO CO O o o o 0 0 0 0 o cr\ vo vo CM LTV rH i—1 iH rH rH CTv CO in m ΙΛ CM Ln rH i—1 i—1 rH rH CU cu a Cu ε ε ε ε < CQ < CQ H H H H rH O 1 sr 1 1 ♦H u •P 1 Ι4Λ r\ •=T ro X 1 CM «o to o (O CO K o o = K X un vo LTV in cu cd ο, cd c — o c p o o 4-5 P o Cu p α rH >5 1—1 c >5 Φ c X 4-5 Φ cu rH X 3 cu -3 CO c o cd Ό co c 4-5 •H CM cd c O o -—. o 3 cd CO c 4-5 Ό Q o O O o O 44> P U •H o α Cu u P o O. φ CO rH ·· I—1 3 X -P C o O o c •H N C o Φ Cm cd •H u > Φ Ή CO Ό rH 1—l P Φ >3 O o E-< K K CO i—I CM co -=T cn * * 5H * :ts tu 4-5 o s c o

C *H

O -P •Η Ή

-P CO

•Η O CO O.

O cu φ ε tu cd ε to cd to Φ £ φ 4-5 .c 4-5 -p cd 4-5 cd cd fn tu cd o. tu cu - m - LV 10023

Table 1 (Cont'd)

42 1 Next, explanation will be given to the produc- tion of the II-A isomer of the triazole compound (II), which is a starting material for the I'-A isomer of the triazole compound (I)·. 5 Method C: Isomerization of the II-B isomer or a mixture of the II-B and II-A isomers of the traizole compound (II)

II-A isomer 0

l! C - r2

Isomeri-zation -> II-B isomer or a mixture of II-B and II-A isomers wherein R23 Rg and n are as defined above.

The II-A isomer can be produced by irradiating 10 the II-B isomer or a mixture of the II-B and II-A isomers with rays from UV lamps or xenon lamps, or experimentally with rays from fluorescent lamps or the sun, in a solvent inert to the rays. As the solvent commonly used, there may be given for example 15 alcohols (e.g. methanol, ethanol, propanol), ethers (e.g. tetrahydrofuran, dioxane), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone), aliphatic hydrocarbons (e.g. hexane, cyclohexane, petroleum ether), and aromatic hydrocarbons (e.g. benzene, toluene, 20 xylene). The reaction may be carried out at temperatures _ ij ? _ LV 10023 1 at which the common photoiomerization is carried out,. but actually temperatures between 0°C and 100°C are preferred. The reaction can of course be carried out with addition of a sensitizer used in the common photo-5 reactions, for example, phenylketones such as acetophenone and propiophenone, but great advantages can not parti-cul'arly be found.

Next, a method for producing the triazole compound represented by the formula (II) will be illustrated. 10 Method D: Production of a mixture of the geometrical isomers of the triazole compound (II) and each isomer (II-B, II-A)

0 ii CHO + CH9 - C 1 ^N ļ IL_ 11

N

N ^TVcH-cJ- Ί (III) (IV) -N (II) vrherein R2, an^ n are as defined above.

The triazole compound (II) is obtained by 15 reacting 1 mole of a ketone of the formula (IV) with 1 to 2 moles of a benzaldehyde of the formula (III) in a suitable solvent in the presence of a basie catalyst. The basie catalyst ineludes for example alkali mētai or alkaline earth mētai hydroxides (e.g. sodium 20 hydroxide, potassium hydroxide, calcium hydroxide), alkali mētai alcoholates (e.g. sodium methylate, sodium 1 ethylate, potassium methylate), carbonates (e.g. sodium carbonate, potassium carbonate), acetates (e.g. sodium acetate, potassium acetate), secondary amines (e.g. diethylamine, dipropylamine, pyrrolidine, piperidine, 5 morpholine) and tertiary amines (e.g. triethylamine, tributylamine, pyridinej picoline, dimethylaniline), and it is used in amounts between 0.01 mole and 10.0 moles. The solvent includes for example alcohols (e.g. methanol, ethanol), aromatic hydrocarbons (e.g. 10 benzene, toluene, xylene), ethers (e.g. diethyl ether, tetrahydrofuran, dioxane)3 water and mixtures thereof.

The reaction is carried out within a range of 0°C to the boiling point of the solvent.

When the basie catalyst is acetates (e.g. 15 sodium acetate, potassium acetate), carbonates (e.g. sodium carbonate, potassium carbonate) or tertiary amines, glacial acetic acid or acetic anhydride can also be used as a reaction solvent.

The triazole compound (II) thus obtainea is 20 a mixture of two geometrical isomers, i.e. II-A isomer and II-B isomer, in general, and each isomer can be isolated by column chromatography or fractional crystallization.

The mixture of the geometrical isomers generally contains a larger proportj.on of II-B isomer than that of II-A 25 isomer. Ali the II-A isomers of the ketone compound are of course novel compounds, and of the II-B isomers, those in which Rj is a l-methylcyclopropyl group are also novel compounds. LV 10023 1 Next, Methods C and D wilļ be illustrated in more detail with reference to the following examples.

Example 4

Synthesis of l-(4-chlorophenyl)-4,4-dimethyl-2-5 (l,2,4-triazole-l-yl)-l-pentene-3^one (Compound No. 1’) by Method D a-(l,2,4-Triazole-l-yl)pinacolone (50 g), anhydrous potassium carbonate (4l g), acetic anhydride (200 ml) and 4-chlorobenzaldehyde (46.3 g) were mixed, 10 and the mixture was heated to 90°C for 12 hours with stirrlng. After cooling the reacion solution, the pre-cipltates were removed by filtration. The filtrate was added dropwise to warm water_(500 ml) of 60°C to decompose acetic anhydride, and potassium carbonate was 15 then added little by little to make the solution alkaline. The produced oily product was extracted with ethyl acetate (500 ml), and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. One drop of the residue. was dissolved in acetone, 20 and the acetone solution was gas-chromatographed under the conditions described below. Then, a peak correspond-ing to the II-A isomer was found at a retention time of 300 sec, and that corresponding to the II-B isomer at a retention time of 360 sec. The ratio of the both isomers 25 was 19.8/61.2, i.e. about 1/3, as calculated from the percentage of each area.

The conditions of gas chromatography was as follows: 46 1

Apparatus:

Column 5

Nippon Denshi 20K gas chromatograph equipped with a FID detector Glass column of 1 m in length liquid phase 5 % ΧΕ-60 carrier Chromosorb W

Temperature Temperature Carrier gas (column) (injection) 200°C 240°C p nitrogen gas. 1 kg/cm

The residue was dissolved in benzene (100 ml). 10 The solution was passed through a column packed with 100- to 200-mesh sllica gel (1.2 kg) and column chromato-graphed with n-hexane/acetone (10:1) as a developing solvent. The fraction corresponding to each isomer was recrystallied from carbon tetrachloride to obtain 36 g 15 (yield 41.6 %) of a pure II-B isomer (m.p. 78 - 79°C) and 10 g (yield 11.5 %) of a pure II-A isomer (m.p. 108 - 109°C). The developing solvent, n-hexane/acetone (10/3), was further passed through the column to recover 8 g of a-(l,2,4-triazole-l-yl)pinacolone. The elementary 20 analysis and NMR spectrum of each isomer are shown below. The NMR sepctrum was measured with deutero chloroform as solvent, and the Chemical shift was expressed by 6 values vrith tetramethylsilane as internai Standard. II-A isomer of l-(4-chlorophenyl)-4,4-dimethyl-25 2-(l,2,4-triazole-l-yl)-l-pentene-3-one (Compound No. 1‘) - 47 - LV 10023 1 Eleraentary analysis: c(%) Η(ί) N(*) Cl(50 Calculated (as C15Hl6N3OCl) 62.17 5.58 14.50 12.23 Found 62.32 5 - 60 14.41 12.20 NMR spectrum: 8.11 (1H, Sj trlazole proton) 7-90 (1H, Sj triazole proton) 5 7.15 (4H, s, phenyl proton) · 6.99 (1H, s, olefin proton) 0.99 (9H, s, butyl proton) II-B isomer of l-(4-chlorophenyl)-4,4-dimethy1-2-(1,2,4-triazole-l-yl)-l-pentene-3-one 10 (Compound No. 1'):

Elementary analysls: C{%) H( J6) N(S) Cl(g) Pound 62.35 5-59 14.38 12.18 NMR spectrum: 8.14 (1H, s, triazole proton) 7.98 (1H, s, triazole proton) 7.22 (2H, d3 phenyl proton, J = 8 Hz) 6.73 (2H, d3 phenyl proton, J = 8 Hz) 7.49 (1H, s, olefin proton) 1.22 (9H, s, butyl proton) 48 - 1

Example 5

Synthesis of the II-A isomer of l-(4-chlorophenyl)-4,4-dimethyl-2-(l, 2,4-triazole'-l-yl)-l-pentene-3-one by Method C 5 The II-B isomer (8.0 g) of l-(4-chlorophenyl) 4,4-dimethy1-2-(1,2,4-triazole-l-y1)-l-pentene-3-one obtained in Example 4 was dissolved in acetone (500 ml) and isomerized at 45°C by means of a ultraviolet ray generator equipped with a 500-W high-pressure mercury 10 lamp. In the course of the reaction, a trace amount of the reaction solution was šometimes sampled and measured for a ratio of the isomers [II-B isomer/ II-A isomer] by gas chromatography under the same conditions as in Example 4. _The results were as 15 followš:

Time (minūte). Ratio of isomers [II-B/II-A] 0 100/0 20 10/90 60 6/94 120 6/94

After 2.5 hours, the reaction solution was transferred to a 500-ml eggplant-form flask, and acetone was removed under reduced pressure to obtain 7.9 g of crystals. The crystals were recrystallized 20 from carbon tetrachloride to obtain 6.2 g (yield 78 %) of crystals (m.p. 108 - 109°C). This compound was dissolved in acetone and gas-chromatographed in the conditions described above, but no peak corresponding - 49 - LV 10023 1 to the II-B isomer was observed.

Example 6

Synthesis of the II-A isomer from a mixture of the geometrical isomers of l-(il-chlorophenyl)-434-dimethyl-5 2-(l,2,4-triazole-l-yl)-l-pentene-3-one (Compound No. 1') The reaction mixture (10 g) containing the II-A and II-B isomers in a ratio of 1 to 3 obtained in Example H was irradiated with ultraviolet rays in the same conditions as in Example 5· After 1.5 hours, 10 the ratio of II-A isomer to II-B isomer was measured by gas chromatography, and it was found that the ratio was about 19 to 1.

After removing the .solvent by evaporation, the crystal obtained was recrystallized from carbon 15 tetrachloride to isolate 5·1 g of the II-A isomer.

Example 7 (A) Synthesis of 3-(^-chlorophenyl)-l-(l-methyl- cyclopropyl)-2-(1,2,M-triazole-l-y1)-2-propene-1-one (Compound No. 29') by Method C 20 l-(l-Methylcyclopropyl)-2-(1, 2,^-triazole- l-yl)ethane-l-one (10 g, 0.06 mole), 4-chlorobenzaldehyde (9 Z, 0-06 mole), anhydrous potassium carbonate (8 g, 0.06 mole) and acetic anhydride (100 ml) were mixedj and the mixture was heated to 100°C for 6 hours with stirring. 25 Precipitates in the reaction solution was removed by filtration, and the filtrate was concentrated under 50 - 1 reduced pressure to obtain an oily product. The oily product was extracted with chloroform (300 ml), and the extract was washed with a sodium hydrogen carbonate-saturated water (300 ml). The organic layer was dried 5 over anhydrous sodium sulfate and concentrated under reduced pressure. One drop of the residue was dissolved in acetone, and the acetone solution was gas-chromato-graphed under the conditions described below. Then, a peak corresponding to the II-A isomer was found at a 10 retention time of 250 sec, and that corresponding to the ΙΪ-Β isomer at a retention time of 300 sec.

The ratio of the both isomers was 19.1/63·5, i.e. about 1/3, as calculated from the percentage of each area.

The conditions of gas chromatography was as 15 follovrs: Apparatus: Column :

Nippon Denshi 20K gas chromatograph eauipped with a FID detector

Glass column of 1 m in length 20

Temperature Temperature Carrier gas liquid phase carrier (column) (inj ection)

5 % ΧΕ-60 Chromosorb W l8l°C 240°C nitrogen gas, 1 kg/cm*

The residue was dissolved in benzene (100 ml). 25 The solution was passed through a column packed with 100 to 200 mesh silica gel (300 g) and column chromato-graphed with n-hexane/acetone (10:1) as a developing - 51 - LV 10023 1 solvent. The fraction corresponding to each isomer was recrystallized from carbon tetrachloride to separate the two entitled geometrical isomers from eāch other. NMR spectrum of each isomer is shown in Table 2. 5 II-A isomer: 1.7 g (yield 10 %) II-B isomer: 6.7 g (yield 38 %) (B) Synthesis of the starting material, l-(l-methyl-cyclopropyl)-2-(l,2,4-triazole-l-yl)ethane-l-one Bromine (28 g) was added to a mixture of methyl 10 l-methylcyclopropyl ketone-[28 g; a well-known compound in Buli. Soc. Chim. Fr., 1708 (1960)], potassium chlorate (5.8 g) and water (70 ml) at 40° to 50°C over 4 hours with violent stirring, and then the reaction solution was stirred at room jtemperature for 2 hours. 15 Thereafter, .the reaction solution was extracted with two 200-ml portions of ether, and the organic layer was dried over calcium chloride and concentratea under reduced ..pressure to obtain 53 g of a crude product, l-(l-methylcyclopropyl)-2-bromoethane-l-one. 20 A mixture of 1,2,^-triazole (18.3 g), anhydrous potassium carbonate (37 g) and acetonitrile (250 ml) was heated under reflux for 1 hour and cooled to 60°C.

The crude l-(l-methylcyclopropyl)-2-bromoethane-l-one (53 g) obtained above was added thereto over 2 hours, 25 followed by stirring at room temperature overnight. Precipitates in the reaction solution was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue obtained was extracted 52 - 1 with addition of water (100 ml) and chloroform (300 ml), and the organic layer was dried over anhydrous magneslum sulfate and concentrated under reduced pressure. The oily residue obtained was crystallized from petroleum 5 ether (100 ml) to obtain 27 g of l-(l-methylcyclopropyl)-2-(l,2,i(-triazole-l-yl)ethane-l-one (yieļd, 57 % based on methyl l-methylcyclopropyl ketone; m.p. 57 - 60°C).

Example 8

Synthesis of the II-A isomer of 3-(il-chlorophenyl)-l-10 (l-methylcyclopropyl )-2- (1,2, Jj-triazole-l-^ 1 )-2- propene-l-one from the II-B isomer thereof by Method C The II-B isomer (4 g) of· 3-(^-chlorophenyl)“ 1-(l-methylcy clopropy 1)-2-( 1^2, ii-triazole-l^l )-2-propene-l-one obtained in Example 7 was dissolved 15 in acetone (500 ml) and isomerized at 45°C for 2 hours by means of a ultraviolet ray generator eouipped with a 500-W high pressure mercury lamp. The ratio of II-A isomer to II-B isomer was measured by gas chromatography under the same manner as in Example 7. It was found that 20 the ratio was 81.2 to 18.1. The reaction solution was concentrated under reduced pressure to obtain 3*9 g of crystals. The crystals were recrystallized from carbon tetrachloride to obtain 2.8 g (yield 70 %) of the II-A isomer. 53 - LV 10023 1 Example 9

Synthesis of the II-A isomer of 3-(^-chlorophenyl)- 1- (l-methylcyclopropy 1)-2-(1,2 , 4-tria-zole-l-yl)-2- propene-l-one from a. mixture of the geometrical 5 isomers thereof

The reaction mixture (3 g ) comprising the II-A and II-B isomers (II-A/II-B = 1/3) obtained in Example 7 was irradiated with ultraviolet rays for 1.5 hours in the same conditions as in Example 8. Thereafter, the ratio 10 of the ĪI-A isomer to II-B isomer was measured by gas chromatography. It was found that the ratio changed from 1/3 to 7/3· After removing the solvent by evaporation, the crystal obtained was recrystallized from carbon tetrachloride to_obtain 1.5 g of the 15 II-A isomer.

Example 10

Synthesis of the II-B isomer of l-(4-chlorophenyl)- 2- (l, 2,il-triazole-l-yl)-l-heptene-3-one (Compound

No. 22) by Method D 20 To a mixture of 2-hexanone (50 g) and methanol (300 ml) was added bromine (80 g) at 0°C, and the mixture was ķept at 10°C for 2 hours. Water (200 ml) and conc. sulfuric acid (50 g) were added thereto, and after s'tirring for 16 hours, water (500 ml) was added thereto. 25 The reaction mixture was transferred to a separating funnel and extracted with ether (500 ml). The organic layer was washed with a 5 % aqueous potassium carbonate - 5*1 - 1 solution and dried over cālcium chloride. The solvent was then removed under reduced pressure to obtain 89 g of crude l-bornio-2-hexanone as an oily product. A mixture of triazole (35 g), anhydrous 5 potassium carbonate (69 g) and acetonitrile (300 ml) was heated under reflux for 1 hour, and allowed to cool to 50°C. The crude l-bormo-2-hexanone (89 g) obtained above was added dropwise to the mixture which was then stirred at room temperature for 16 hours. Precipitates 10 in the reaction solution was removed by filtration, and solvent was removed under reduced pressure. To the residue obtained were added water (200 ml) and chloroform (200 ml), and the mixture was transferrea to a separating funnel, followed by extraction. The organic layer 15 was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain 77 g of crude l-(l,2,il-triazolyl)-2-hexanone as an oily product.

The resulting 1-(1,2,i|-triazolyl)-2-hexanone (20 g), anhydrous potassium carbonate (20 g), p-chloro-20 benzaldehyae (20 g) and acetic anhydride (200 ml) were mixed and heated to 90°C for 5 hours. The reaction mixture was then concentrated under reduced pressure, and then the residue was dissolved in ethyl acetate (500 ml) and transferred to a separating funnel. 25 The ethyl acetate solution was washed with a potassium carbonate-saturated water (200 ml), and the organic layer was separated. The solvent was removed from the organic layer under reduced pressure, and the - 55 - LV 10023 1 residue was placed on a silica gel column (0.5 kg of . 100 to 200 mesh silica gel) and column chromatographed with a n-hexane/acetone (10:1) mixture as a developing solvent. Thus, 3.7 g of the II-B isomer (m.p. 117° -5 120°C) of l-(i}-chlorophenyl)-2-(l,2.,ļ4-triazo.le-l-yl)- l-heptene-3-one and 9 g of 1-(4-chloropheny1)-2-(1,2,A-triazole-l-yl)-3-acetoxy-l,3-heptadiene (m.p. 112° -113°C) were obtained. ' .

To the resulting l-(4-chlorophenyl)-2-(l,2,4-10 triazole-l-yl)-3-acetoxy1-1,3-heptadiene (9 g) was added conc. hydrochloric acid (100 ml), and the mixture was heated to 50°C for 2 hours and pourea into ice water (500 ml). The aqueous liquor was neutralized with potassium carbonate and extracted with ethyl acetate. 15 (300 ml). The organic layer was dried over anhydrous

I magnesium sulfate, and the solvent was removed by evaporation. The crystalline residue was recrystallized from a carbon tetrachloride/n-hexane (1:1) mixture to obtain 6 g of the II-B isomer of l-(4-chlorophenyl)-20 2-(1,2,4-triazole-l-yl)-l-heptene-3-one.

Example 11

Synthesis of the I-A isomer of l-(2,i!-dichlorophenyl)-2-(l, 2, il-triazole-l-yl)-it, A-dimethyl-l-pentene-3-ol (Compound No. 2)

25 Pirst step (condensation) Method D A mixture of a-(l,2,4-triazole-l-yl)-pinacolone (200 g), 2,4-dichlorobenzaldehyde (220 g) and acetic - 56 - 1. anhydride (700 cc) was heated to 50°C, and triethylamine (255 g) was added thereto. After keeping the temperature at 70°C for 7 hours, acetic anhydride was removed under reduced pressure. Water (3 liters) was added to the 5 residue, and the resulting crystals were eollected by filtration, washed with water and dried. The crude product obtained was recrystallized from ethanol (600 cc) to obtain 30^1 g of the II-B isomer of l-(2,il-dichloro-pheny1j-2-(1,2,4-triazole-l-y1)-4,4-dimethy1-1-10 pentene-3-one (Compound No. 2').

Second step (Photoisomerization) Method C

The II-B isomer (300 g) of Compound No. 2’ obtained in the first step was dissolved in acetone (2 liters) and isomerized at-30°C for 2β hours by means 15 of a ultraviolet ray generator equipped with a 500-W high-pressure mercury lamp. The solvent was theņ removed under reduced pressure to obtain 300 g of an oily product. It was found by gas chromatography that this product was a mixture comprising 75 % of the II-A 20 isomer of Compound No. 2* and 25 % of the II-B isomer of the same compound. This product was transferred to the next step vrithout separating each isomer.

Third step (Reduction) Method A

The mixture (300 g) of the geometrical isomers 25 of Compound No. 2' obtained in the second step was suspended in methanol (1 kg), and sodium borohydride (38 g) vras added thereto in portions while cooling the reaction mixture to 10°C. After stirring at room - 57 - LV 10023 1 temperature for 1 hour, the reactioņ solution vras concentrated under reduced pressure. The residue obtained was extracted with addition of 10 % aqueous acetic acid .solution (2 liters) and ethyl acetate (3 liters). The 5 separated organic layer was washed with 5 % aqueous potassium carbonate solution (1 liter) and dried over anhydrous magnesium sulfate (100 g). After removing the drying aģent by filtration, the solvent was removed under reduced pressure to obtain 280 g of a crude 10 product as crystals. This product was a mixture of the I-A and I-B isomers .of Compound No. 2 (mixing ratio: I-A/I-B = 75/25)· The crude product (280 g) was recrystal-lized from carbon tetrachloride (600 cc) to obtain 209 g of the entitled compound (Ι-,/Lisomer of Compound No. 2). 15 The mother iiquor from recrystallization was concentrated to a half to obtain 25 g of the I-B isomer of Compound No. 2 as secondary crystal.

The II-A isomers of the ketone compound (II) obtained by Methods C and D are shown in Table 2 together 20 with the II-B isomers. NMR spectrum in the table is indicated in the same form as in Table 1. - 58 -

CM

Table εd Sh -po d)Cuwod2 CM Od 0 — 0 o— 2H \i2o

Olefin proton 0 II -CH = C - C - 6.99 CTv -=Γ CM CM VO -=Γ’ t^~ CM <Η C— οο οη C-- CM ΟΛ νο 1 Η SK C~- =Γ s-' • Ε C~~ '— CO -=Γ C— φ ο οο Ο ο ιη νο νο -=Γ t—i σ\ ΟΛ «=Γ οο ο 00 ο αν o c • • ~ • • • • • N O C— CO t>- CO c-- CO >- Cti O •H 0 *\ «V Λ * U ?H Η *=r ο -=Γ ιη CM CO CO Ch (Η (Η οη cr\ CM Ο CM ο οο οο CO CO ΟΟ CO οο ο ο Ο Ο Ο Ο ο 00 0 0 0 0 0 0 0 νο r-i 4-3 σ\ σ\ οη ο ιΗ -=Γ γΗ ιη cd c ο c— C?V CM οη σ\ ιη o cd ιΗ 1—1 ι—1 • •H O I ι 1 1 I ι 1 ι—1 w w οο CO CM σν CTV οη σ\ >3 c σ c~- σν ι—1 CM σ\ νο LH JZ o ι—1 I—1 ρ-Η • 0-1 o —4 α α α ο. α α Ρ. CMQ Ε ' ε Ε Ε Ε Ε Ε C <H 1 _ Ο O ®H (!) < ω < ω < 2 < α Td E cd ε 1 ι I ι 1 • 1 1 I C o o o Η Η Μ 1—1 Μ Η Η Η Ή ® rl (D Η Η Η Μ Μ Η Μ Η 2 bO P -H C Γ Η ο on 1 Od 1 Η Ό γΗ 1 Η ο 03 Λ 1 1 -=Γ CM οη CM /—> od οη 2 r Ο Ο Ό 1 c · Μ — E 3 O ιΉ CM οη -=Γ 0 0 2 ο α

Cont' d - 59 - LV 10023

Table 2 (Cont'd)

Cont1 d - 6o -

Table 2 (Cont'd) o „ OJ 0- C0 (Μ «Η ΟΟ -=Γ ι—1 ιη VO ο ιη νο -=Γ 1 Η νο CM ιη Ο VO CM *=Γ ι—1 νο ι—1 ιη CM ιη * * 9 ln ι— . 0- C— C— C-- 10- c- c- C— ο- C— C— • Ē C— «5T ι—1 σν γΗ ι—1 νο CO σν οο οο C— ιη σν ιη o σ\ ο σν σ ο Ο σν ο ο ο σν ίΗ ι—1 00 ο- CO t— οο 00 00 0- οο οο οο C— 00 CO r\ «\ Λ η «V Λ 91 #1 -=r CO Ο VO CM Ο Ο ιη νο ο ο οο οο ο m ο οο Ο CM CM οο 1—1 CM CM οο 1—[ CVJ OJ r 9 co CO 00 CO CO CO 00 00 CO ΟΟ CO CO οο ΟΟ o ο ο Ο Ο ο ο Ο Ο ο ο ο 0 0 0 0 0 0 0 0 0 0 0 0 in VO CM οο οο ιη «=Γ 00 0- VO 00 CT\ VO 00 Η Η Η ι—! c^- νο C0 ο t—1 νο γΗ ιΗ Η γΗ ιΗ νο ιΗ 1 1 1 I ι 1 I 1 1 1 ιη 1 1 oo 0J ιη Η C\i ο -=Τ οο CM 0- • ΖΤ ιη σ\ VO CO γΗ ιΗ ΟΟ γΗ ιΗ νο 00 ι—1 ίΗ νο γΗ ιΗ ι—1 * ι—1 «—1 Η CM α α α α α ο. α α Ο. α (MQ α α ε ε ε ε ε ε ε ε ε ε C ε ε < ΡΡ < ΡΡ < ΡΡ < ΡΡ < ΡΡ < ΡΡ < ΡΡ Η Η Η Η Μ Μ Η Η Η Η Η Η Η Η Η Η Η Η Μ Η Η Η Μ Μ Η Μ Μ Η ι—1 ·· >5 C ΟΟ ω X ΟΟ CM tH χ Ο «»u Ο ο (X Ο Ο X ο X CM -=Χ -=Γ -=Γ ΟΟ s ΓΟ χ — — — — ο V-/ Ο ιη VO 0- CO ον ο (Η ι—1 rH

Cont1 d 61 LV 10023

Table 2 (Cont'd)

Cont(d 62

Table 2 (Cont1d) CM o OD crv VO vo LTV O vo CM ov cn vo o CM co 1 H Lf\ •=r t— m t— -=T c- CM cn 1 H in * * • O t— c— t" c— t>- c— c*- t- c— co c- -=T ^ rH ^ • E • E c— o. CO 00 vo LH t— vo -=r in cn co o cr\ o o o o o o o CTN o o co oo 00 oo co co oo co co oo co Λ ** Λ Λ *\ Λ *\ «V o O σ\ rH LTV o CM o t- CM in cn CM CM m CM cn CM cn CM CM rH CM CM oo CO co CO oo 00 co co co oo 00 00 O ϋ o o o o o 0 0 0 0 0 0 0 i—1 rH vo o cn 00 rH rH in c— rH o CM vo CM c— o co o rH rH rH rH o rH rH rH CM H VO 1 1 1 vo 1 1 1 tn LPc i in o co -=r • CM VO o • • VO • o cn cn CM rH CM c- o rH rH rH H rH * rH rH rH rH •ΞΓ cn in vo α α α CM Q α α 0* CMQ CMQ O. CMQ E E E c E E E c c E C < cα < 02 < 02 < 02 < 02 < CQ M M M H H H M H H H H M H H H H H H H H H H H H cn >> T X o O o c 1 cu cn £ rH rH rH Ph 1 o* o o o o -rr -=r - 1 Γ 1 cn m ΓΟ CM CM cn cn cn X E E E cn o — — o o o cn X O cn Ne/ \x/ E o ” X o o o o • o r CM cn - in vo c— j—1 rH rH rH rH rH

Cont' d 63 LV 10023

Table 2 (Cont'd)

Cont1 d - 6b -

Table 2 (Cont'd) tn rH 00 CO MO m vo O 0 m O CM LO CM CT\ co ¢-- co c— ļ H VO * • c— t— C" c— c- C-~ t— c— 0 C— -ΞΓ • E in 0 OJ C- o\ 0- co H -IT co m • 0 OV co C7\ OV . 0 0 0 σν 00 • OD t» 0· o- t— 00 co 00 t— 1 cm ^ · 5(5 Α A A A Λ A A A A D~-C\l vo 00 CO f- LTV 0 O LTV CT\ CO OJ 0 CM 0 OJ rH co OJ CO O • · Ē • • • • • • • • • . CO CO — co OO co co co co 00 co CO O 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0 -=T OJ vo 0 c— 0 CM .=r co C\l O LT\ vo vo OJ CO co rH rH 0 1 1 rH 1 1 —J tn in 1 1 1 1 H rH • • « ΙΠ t— rH co co CM CTV co uo CT\ vo rH co co 1—I rH CO * in ir\ rH α α α α α α α α X ε E E E E E E E E < X C pa < X < X < X Η H H H H H 1 H H H H Η H H H H 1—i H H M H OJ Ο rH X 0 ir\ CO 1 X Ό rH O rH rH 1 ο O 0 0 CO 1 , A OJ CM -ξγ CM CO co X X 0 CO 0 CO CO /-S OJ co s rv CO X X OJ co X 0 0 X X ο 0 O O V-> V-/ 0 • 0 00 σ\ 0 1—1 CM rH 1—1 CM OJ CM

Cont ’ d 65 LV 10023

Table 2 (Cont'd)

Cont1 d 66

Table 2 (Cont'd) O O C-- X vo c— oo o σν O CO 1—l oo in .CM σν X o VO CM c— 1 I—1 vo oo c— 1 iH σν •, • • « • • * • * • * • f- o- r- o- tv- o C-- 0- 0- OV t- OO^N • ε • ε t>-w co oo oo o LTV σ\ σν i—1 LTV o VO σν σν CTV o o O σν σν o o o o σν c^- c— 00 co CO c- co 00 co co c— n *\ r\ r» «» o «\ *» vo vo 0- C- -=X co o oo rH o X X X I—1 CM i—I oo rH CM i—l oo X oo rH CO oo oo oo OO co OO co co oo co co vo o O o o o o o i—i 0 0 0 0 0 0 0 VO CM CM CM o tv- oo oo rH 0- σν un vo VO o- co co co σν rH co co • irv vo i—1 0- Ή 1 I LT\ 1 1 1 irv 1 in 1 o σν • co vo X • o • co LTV vo in r-ļ 0- CO OO oo rH rH rH CO * * i—I oo -=T -=T »r CM Q a a CMQ a a a X Q a X Q a c ε ε C ε ε ε C ε C ε < CQ < X < X < X < X < X H H H H M H H I H 1 H H H H H H H H H M H H M H H H CM rH OO o X LTV O X •H V_> CM Ό «H X rH O rH o o o o o .=r -=r «ΞΓ ’ -=X —J X CM oo /-S X OO OO OO o X |-r X un OO o oo o o v_x X oo X CM OO a oo X X X 5 a o X o o o o o CM o X \S/ s—' a X cr • o o o o oo -=T in vo c— 00 CM CM CM CM X X

Cont1 d 67 LV 10023

Table 2 (Cont'd) Λ s /^N £ Ē N N X Λ •τ-t X r- vo CO co '—' II II o o h» o o • • Λ rs rH (—l Ό Ό I 1 *\ Λ X X o o VO vo CO o -—> v-' • • 1—I O i—1 OJ o CM C— in • • CO 05 Λ H i—i • • /^S <**“N .'-s o o N N N N X X X X *» /-s /-s co in c— m ε ε II II II II *> X X hi ►o 1-5 co co ^—' V_/ Λ Λ *> «\ -P -P •P -P o o o o Λ *> «5 Λ • • X X X X Ol OJ OJ co oj co ------ 1 1 VO Ln OJ co o o co inco in vo • · • · • • OJ o OJ o Ol OJ Λ X co i—1 /-N o €\ r\ • t-i-4 /—s ✓—\ rH ε ε ’t- Λ *> Λ || s X £ £ CM ΟΙ *O V— Λ »-1-4 ^ ^ X « o ο CM N CVJ p) CO -ΖΓ s-^ X • • rs rH Η o c— O X OJ -=r co 1 1 • II • ^ rH 1—1 o ο OJ CTn ο 1 1 05 CM • • Λ • CM i—1 ΟΙ O *P o o * co 05 rH Λ r\ • *> • o 4-—·* N r—N rH K i—1 ·* ' N N tsl Ν CO N X X χ un *—r "X *-- /—s o-1>- C— ε co ε c— 15- II II 11 II Λ · " II X o X *“D *“3 *“3 l“D 1—1 H 1-5 ✓ «1 #> *\ o /-*S n -P -P •P -P O N Ο Ό O X ln r» *\ n r> • • r\ W*M tM hH Ν·*|"Ι · X X OJ ο Ο: X OJ OO OJ co CO w w ι II 1 w tn in O OJ O 1-5 o o -=T oo in co LT\ rH OJ • · • · • r\ • OJ o OJ o OJ Ό CO iH i i Cont ’ d 68

Table 2 (Cont'd) o o CM CA C— vo ca LT\ VO vo 1—1 vo LA rH LA 1 H c- rH la I rH vd CM VO • • * • • • * • • • C-- C"- co t- t- t- o C'- <=r ^ <=T • £ .* £ t>-w co t"- CO LA CM LA t— LA CA CO o o O «\‘ o o o o o o • « • X • • • • • • co oo co CM co co co co co co n «N «N «N Λ Λ «\ +s co CM LA o vo 00 la o =r CM rH CM i—1 CM i—! co rH co . rH • • • • • • • • • • CO co OO co co oo co co co co o o o o o 0 0 0 0 o 0 CM LA CO o 0 -=T co CM CM σ\ CTv C— CO CA CA C— 00 VO -=r -=T co \o vo co oo 1 1 1 1 1 1 la in LA la o\ rH ca co oo • • • co c— co 00 co o- rH rH rH rH c— vo c— vo α Oi O. O, α α CM Q CM o CM Q CM Q ε £ £ £ £ ε c c c c < m < CQ < m < CQ < CQ 1 Η H H H H H H H H H Η M H HH H H H H H H Γ“ u •H Ό rH u ο -=T X 1¾ X Λ 1 -=Γ CM -=r cr CM X ο ρη \ OJ X \x Ο O Ξ. ZL / Ο Ι CA c 5 i—1 CM co CM m co co co

Cont'd 69 LV 10023

Table 2 (Cont*d)

Cont1 d 70

C . o c •H o -P •H . *H -P CO •H O CO a O a cd E (D cd E co cd co ω Φ -P •P -P cd 4-5 cd U cd U cd cd a <D a a cd a cd C o G -P o o -P G o a u a 1—i >3 rH C >3 CD c 2 0) a 2 a Ό C Ό cd c 4-3 cd C O o 3 C 40 Ό O O O -P U G o a a u a CD co rH 3 c o O iH N C cd •rH CD Ή CO rH G CD O ĒH rH CM oo * * * cd 4-3 o

Table 2 (Cont'd) [" CT\ la o σ\ σ\ * MD rH co o la o IA V£> rH LA rH LA • • • « 1 * • « • c— c— c— o- O C- 0- c— oo-~ • E 0"- -=r -=r o LA rH vo vo o rH o CT\ O o o o co co co tr- co co co co A A «\ A a Λ A A cn CM LA cn rH rH rH cr\ CM OO CM rH oo rH oo rH oo CO co co co co co co O O o o o 0 0 0 0 •0 la CO co -=r co CM LA co o CA o c— 0- t>- rH rH LA o la 1 1 1 1 1 IA 0 • r~- c~- OO t— rH • oo i—i o 0- o\ o rH o i—1 rH rH o o CM Q a a a a a CMQ a C E E E E E C E <' CQ < m < CQ < C0 M M H H H H M H H H H H H H H H i—l 1 •H o rH u -P •r H LA 1 1 K -=T LA CM 1 A 00 LA o -=r |7"| A 1 A o oo -=r CM co O cn cn -r r ~ o M_/ o 1 - LA LO o- cn cn OO oo 71 2 LV 10023

Table 2 (Cont'd)

72 1

In the practical application of the present compounds thus obtained, they may be used alone without other components or in a mixture with carriers for the ease of use as a fugicide, herbicide and plant growth 5 regulator. The commonly used preparation forms include for example dusts, wettable powders, oil sprays, emulsi fiable concentrates, tablets, granules, fine granules, aerosols and flowable preparations.

The foregoing preparations generally contain 10 0.1 to 95-0 % by weight of active ingredient (including other ingredients mixed). A suitable amount of active ingredient applied is generally 2 to 500 g per 10 are, and the concentration of active ingredient applied is preferably within a range of_0.001 to 1.0 %. Since, 15 however, the amount and concentration depend upon the preparation forms, application times, application techniques, application sites, diseases and crops, they may properly be increased or decreased irrespective of the aforesaid ranges. 20 In formulating the fungicide, herbicide and plant growth regulator of the present invention, suitable solid carriers or liquid carriers are blended. As the solid carriers, there may be given for example inorganic substances (e.g, clays represented by 25 kaolinite group, montmorillonite group or attapulgite group, rtalc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium, lime, apatite, zeolite, silicic acid - 73 - LV 10023 1 anhydride, synthetic calcium silicate), vegetable organic substances (e.g. soybean powder, tobacco powder, walnut powder, flour, wooden powder, starch, crystalline cellulose), synthetic or natūrai high molecular weight 5 compounds (e.g. coumarone resins, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum, dammar gum), and waxes (e.g. carnauba wax, bees wax), and urea.

As the liauid carrlers, there may be given for 10 example- paraffin or naphthene hydrocarbons (e.g. kerosene, mineral oil, spindle oil, whlte oil), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene), halogenated hydrocarbons (e.g. carbon tetrachloride, chlorof-orm, trichloroethylene, 15 monochlorobenzene, o-chlorotoluene), ethers (e.g. dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone), esters (e.g. ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, 20 dibutyl maleate, dlethyl succinate), alcohols (e.g. methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol), ether alcohols (e.g. ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol 25 butyl ether), polar solvents (e.g. dimethylformamide, dimethyl sulfoxide) and water.

As surfactants used for emulsification, dispersion, wetting, spreading, binding, regulation of _ 7ίι _ 1 disintegration, stabilization of active ingredient, flowability improvement and anti-molding, any one of nonionic, anionic, cationic and amphoteric surfactants may be used, but generally nonionic and/or anionic ones 5 are used. As suitable nonionic surfactants, there may be given for example those obtained by polymerizing ethylene oxide and a higher alcohol (e.g. lauryl alcohol, stearyl alcohol, oleyl alcohol), ethylene oxide and an alkylphenol (e.g. isooctylphenol, nonylphenol), ethylene 10 oxide and an alkylnaphthol (e.g. butylnaphthol, octyl-naphthol), ethylene oxide and a higher fatty acid (e.g. palmitic acid, stearic acid, oleic acid), ethylene oxide and a mono- or di-alkyl phosphate (e.g. stearyl phosphate, dilauryl phosphataJ, or ethylene oxide and an 15 amine (e.g. dodecylamine, stearic acid amide), higher' fatty acid esers of a polyhydric alcohol (e.g. sorbitan) and those obtained by polymerizing said esters and ethylene oxide, and ethylene oxide/propylene oxide polymers.

As suitable anionic surfactants, there may be given for 20 example salts of an alkyl sulfate (e.g. sodium lauryl sulfate, amine salts of oleyl sulfate), alkylsulfonates (e.g. sodium salt of dioctyl sulfosuccinate, sodium 2-ethylhexenesulfonate) and arylsulfonates (e.g. sodium isopropylnaphthalenesulfonate, sodium methylenebis-25 naphthalenesulfonate, sodium lignosulfonate, sodium dodecylbenzenesulfonate).

Further, the preparations of the present compound may contain high molecular weight compounds and 75 - LV 10023 1 other assistants, in order to improve their performances and biological activity. The high molecular vreight compounds include for example casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl 5 cellulose, hydroxyethyl cellulose and polyvinyl alcohol.

The foregoing' carriers and assistants are properly used alone or in combination according to interided uses, taking into account preparation forms and application techniques. 10 The content of .active ingredient in the dusts is generally 1 to 25 parts by vreight, and the rest is a solid carrier.

As to the vrettable powders, the content of active ingredient is generally 25 to 90 parts by vreight. 15 The rest is a solid carrier and a dispersion-vretting aģent, and if necessary a protective colloid, a thixo-tropic aģent and an anti-foaming aģent are added thereto.

As to ‘the granules, the content of active ingredient is generally 1 to 35 parts by vreight, and most of 20 the rest are a solid carrier. The active ingredient is uniformly mixed vrith a solid carrier, or it is uniformly fixed or aasorbed to the surface of the solid carrier.

The pārticies are about 0.2 mm to about 1.5 mm in diameter.

As to the emulsifiable concentrates, the content 25 of active ingredient is generally 5 to 30 parts by vreight, an emulsifier occupies about 5 to about 20 parts by vreight, and the rest is a liauid carrier. If necessary, anti-mold aģents are added.

Further, the compounds of the present invention - 76 - 1 may be applied in a mixture with other fungicides, herbicides and plant growth regulators vrithout lowering the controlling effect of each active ingredient of the mixture. As the fungicides, there may be given 5 N-(3,5-dichloropheny1)-1,2-dimethylcyclopropane-1,2-dicarboximide, S-n-butyl S-p-tert-butylbenzyldithio-carbonimidate, 0,0-dimethyl 0-(2,6-dichloro-4-methyl-phenyl)phosphorothioate, methyl l-butylcarbamoyl-lH-benzimidazole-2-yl-carbamte, N-trichļoromethy lthio-*}-10 cyclohexene-l,2-di'carboximide, cis-N-(l,l,2,2-tetra-chloroethylthio)-4-cyclohexene-l,2-dicarboximide,

Polyoxin, Streptomycin, zinc ethylene-bis(dithio-carbamte), zinc dimethylthiocarbamate, manganese ethylene-bis(dithiocarbamatej., bis(N,N-dimethylthio-15 carbamoyl)disulfide, tetrachloroisbphthalonitrile, 8-hydroxyauinoline, dodecylguanidine acetate, 5,6-dihydro-2-methyl-l,4-oxathiine-3-carboxanilide, N'-dichlorofluoromethylthio-N,N-dimethy1-M1-phenylsulfamide, 1- (4-chlorophenoxy) - 3,3-dimethy 1-1- (1,2, ii-triazole-l-yl)-20 2-butanone, l,2-bis(3-methoxycarbonyl-2-thioureido)- benzene, methyl N-(2,6-dimethylphenyl)-N-methoxyacetyl- 2- methylglycinate, aluminum ethylphosphite and the like.

As the herbicides, there may be given phenoxy series herbicides such as 2,4-dichlorophenoxyacetic acid, 25 2-methyl-4-chlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and 2-methyl-4-chloro-phenoxyacetic acid (including esters and salts); diphenyl ether series herbicides such as 2,tl-dichlorophenyl 77 - LV 10023 1 4'-nitrophenyl ether, 2,4,6-trichlorophenyl 4'-nitrophenyl ether, 2-chloro-4-trifluoromethylphenyl 3'-ethoxy-4 nitrophenyl ether, 2,4-dichlorophenyl 4'-nitro-3*-methoxyphenyl ether and 2,4-dichlorophenyl 3,-methoxy-5 carbonyl-4 ,-nitr.ophenyl ether; triazine series herbicides such as 2-chloro-4,6-bisethylamino-l,335-triazine, 2-chloro-4-ethylamino-6-isopropylamino-l,3 3 5-triazine, 2-methylthio-4,6-bisethylamino-l,3,5-triazine and 2-methylthio-4,6-bisisopropylamino-l,3,5-triazine; 10 urea series herbicides such as 3-(3,4-dichlorophenyl)~ 1,l-dimethylurea, 3- (3 3 4-dichloropheny1)-1-methoxy-l-methylurea, l-(a,a-dimethylbenzyl)-3-p-tolylurea and 1-(2-benzothiazoly1)-1,3-dimethylurea; carbamate series herbicides such as isopropyl N-(3-chlorophenyl)-15 carbamate and methyl N—(334-dichlorophenyl)carbamate; thiolcarbamate series herbicides such as S-(4-chloro-benzyl) N,N-diethylthiolcarbamate. and S-ethyl N,N-hexamethylenethiolcarbamate; acid anilide series herbicides such as 334-dichloropropionanilide, 2-chloro-20 N-methoxymethyl-2',6'-diethylacetanilide, 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide, 2-chloro-2',6'-diethyl-N-(n-propoxyethyl)acetanilide and M-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester; uracil series herbicides such as 5-bromo-3-sec-butyl-6-25 methyluracil and 3-cyclohexyl-536-trimethyleneuracil; pyridinium salt series herbicides such as l,l'-dimethyl-4,4'-bipyridinium chloride; phosphorus series herbicides such as N-(phosphonomethyl)glycine, N,N-bis(phosphono- - 78 - 1 methyl)glycine, 0-ethyl 0-(2-nitro-5-niethylphenyl) N-sec-butyl phosphoroamidothioate, S-(2-methyl-l-piperidyl-carbonylmethyl) O,0-di-n-propyldithiopriosphate and S-(2-methyl-l-piperidylcarbonylmethy1) 0,0-dipheny1-5 dithiophūsphate; toluidine series herbicides such as α,α,α-trifluoro-2,β-dinitro-N,N-dipropyl-p-toluidine; 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-l,3>4-oxadiazolin-2-one; 3-isopropyl-(1H)-2,1,3-benzothiadiazine (3H)-one-2,2-dioxide; a-(3-naphthoxy)propionanilide; 10 (2,4-dichlorobenzoy1)-1,3-dimethylpyrazole-5-y1 p-toluenesulfonate; 3-(methoxycarbonylamino)phenyl 3-methylphenylcarbamate; 4-amino-3-niethyl-6-phenyl-1,2,4-triazine and the like.

Also, the compounds_ of the present invention may 15 be applied in a mixture with other insecticides vrithout lowerlng the controlling effect of each active ingredient of the mixture. As the insecticides, there may be given organo-phosphorus insecticides such as 0,0-dimethyl 0-(4-nitro-3-methylphenyl)phosphorothioate, 0-(4-20 cyanophenyl) 0,0-dimethylphosphorothioate, 0-(4-cyano-phenyl) 0-ethylphenylphosphonothioate, 0,0-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate, 2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide and 0,0-dimethyl S-(l-ethoxycarbonyl-l-phenylmethyl)phosphorodithioate; 25 and pyrethroid series insecticides such as a-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)isovalerate, 3-phenoxy-benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-carboxylate and a-cyano-3-phenoxybenzyl 2,2-dimethyl- - 79 - LV 10023 1 3-(2,2-dibromovinyl)cyclopropanecarboxylate. Consequently, two kinds or more of disease and pest can be controlled at the same time, and further a synergistic effect owing to mixing is expected. 5 Next, the usefulness of the present compounds as fungicides, herbicides and plant growth regulators for agriculture and horticulture wlll be illustrated more clearly with reference to the following tēst examples and preparation examples.· 10 Tēst Example 1

Fungitoxic effect A medium containing 5 g of polypep'cone, 20 g of malt extract, 20 g of sucrose and 20 g of agar per 1 liter of water, was turned into a solution by heating. 15 The aqueous dilute liauor of the emulsifiable concentrate of each tēst compound was added thereto so that the concentration of the tēst compound in the medium was a pre-determined one. After thoroughly stirring the medium, the medium was poured into a glass Petri dish to make an 20 agar plate. After the agar solidified, it was inoculated with the mycelial disc or spore suspension of a tēst fungus. The name of the tēst fungus and a culture period from inoculation to observation are as shown below. The culture temperature was 20°C for Venturia 25 inaeaualis and 28°C for other fungi. - 80 -

Name of fungus Abbrevia- Culture tion period Helminthosporium gramineum Hs 6 days Penicillium italicum Pi 6 days Venturia inaeaualis Vi 7 days Valsa mali Vm days Mycosphaerella melonis Mm 4 days Diaporthe citri Dc 6 days Ustilago nuda Un 6 days Verticillium albo-atrum Va 7 days Septoria tritici St 7 days Cercospora beticola Cb 7 days Fusarium oxysporum f. sp. lycopersici Fo 4 days Alternaria kikuchiana Ak 4 days 1 The degree of growth inhibition of the tēst compounds was evaluated in four ratings A, B, C and D: A: Degree of growth inhibition 100 Cf >5 B: ir 90 ef /9 or more C: II 89 50 % D: II 40 cf JO Or less

As shown in Table 3j it was found that the I-A isomer of the present invention has a markedly broad antimicrobial 5 spectrum as well as a remarkably high activity as compared with the I-B, II-A and II-B isomers.. -81- LV 10023

Table

1 1 t I I | | 1 | [ 1 I <c o 1 I 1 1 1 1 I I I I 1 ļ | | 1 ( fil Cb cd < <=d <d < o pa pa < pa pa o cd pa o o pa pa ' c o Ί| .> co cd < < o < c cd o cd cd o pa cd pa pa pa pa o •H •P «H •H Va < o < o o o o o o o o o o o o o o o C •H s: •P Un P) o o o o o o o o o o o o o o o o o o Sh &0 Dc < c < < pa p: pa pa pa pa pa pa o pa o pa pa cd tin o 0 Mm < < < o < o <d o pa <d pa pa o pa pa pa pa pa 0 u faO ω Q Vm < < < o < < o o o pa o o <d o pa pa pa o Vi < < < o < cd cd pa < < pa pa pa pa pa pa pa cd 0-, < < < < c pa cd pa pa cd oa o o pa pa pa pa o w X < < < CQ < o pa pa pa cd pa pa pa pa oa pa pa <d c o *rn •p -i P ca cd c ^ Jh > Φ Ē U -H · ri α Ln o LTi - ” - - c^ti α CM <u o <u ^ o cd u c aO O <P c o o . H <P ό rH CM cn -=r m co C- CO ON o t—t CM cn -=r lf\ co e— CO £2 i—1 ("Η i—i rH rH 1—i rH rH rH 0) d ε ό c o c d co d o •H 0 P α 0. n £ < ε Φ o I o E* o Η O

Cont *d 82 i i i i ι cq ο ι ι cq cū ffl ca in ffl i i 'i

Cont1 d

I I I I I CQ Ο I IO CQCQCQOOCQ<CQ

CQ CQ 00000CQ<0 I I I I I CQ Ο O I <O<<<<<<<< <C<<<<>a;<=iCQ cqoooooocq<o ffl ffl ffl ο ϋ ι ι i

oooooooo<o I I I l I I l I ffl(QtQCQūfflfflCQ<0 eč<<CQCQ<CQCQ

Table 3 (Cont'd)

CQCQOOOCQOCQ<0 < < < CQ CQ I I I CQO<<<OOCQCO I I I I I < < <

<CQ<<<<<<<< <<<<<<<CQ

CQCQOOOOCQ<<< <<<CQCQCQOO

CQCQ OO OCQ<< << <<<CQCQCQCQCQ

Ln o CTsO ι—I CM ΓΌ -=T inOC-CO CTvO H CM ΓΠ -=r inoco i-<cHCM CMCMCMCMCMCMCMCMCMmpnmOOCOCO-=r-=r ω E Ό 0 c W d

Ou

< E 1 o

Η O 83 LV 10023 I I I I I I I I I I I I I ι ι ι ι ι ι . . χ)

I I I I I I I I I I I II ! I I I I I -P c o --“- 0 OPDPPPPPPPPPPPPPPPP l OPPPPPPPPPPPPPPP'PPP opppppppppppppppppp

PPQQQQQPPPQQQPQPQPP

P P P P P P P P P P P P P P P P P P P T3 P £ O P P P P P P P P P P P P P P P P . P P P P v._s ro P P P P P P P P P P P P P P P P P P p' <D rH P aJ P D P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P

QQQQQQQDQQQQPPQPPPP LT\ O LT\ = = =

OJ

P o H OJ £ tu.—> ω Ο Ό E T3 c c 0 c 0) 3 co 3 £ O ai a Ά ρ E CQ E Φ o 1 o K o Η O

r- co σ\ o ι—I ri w ro j in vo ι—t i—I —I ι—I ι—I —t

n co cn I—I I—I I—I - 8i* -

I

I I I I P P I I P P P P P P I I I I l I I

Cont · d

I I I I P P I IPPPPPP'PP I I I I I PPPPPPPPPI I I I IPP ppppp PPP PPPPPPPPPPPPP p pppp PPPPPPPPPPPPPPI I ppppp

PPPPPPPPPI I I I I I I PPPPP

PPPPPPPPPPPPP PPP PPPPP

Table 3 (Cont'd)

PPPPPPPPPPPPPPI I PPP PP ppppppppp | | | | I OP PPPPP ppppppppppppppop ppppp PPPPPPPPPPPPPPPP ppppp PPPPPPPPPPPPPPPP PPPPP ia oo U CM (D £ Όo c

I—I CM

CM CM

co CM

=r CM

LA CM

vo CM

CM

co CM oon ΓΟ CMoo COcn =rco cn ΓΟ co

u ωε η Ο C CM CO ·=Χ ΙΑ 3o αεο

CQ I Η O

ω Ή< I 3ο αεο Η Ο Η 85 ILV 10023

I I I I Ί I I I I I I I I I I I I I I I I

I I I I I I I I I I I I I I I I I I I I I

Cont1 d PPPPPPPPPPPPPPPPPP PPP i

Ρ ΡΡΡΡΡΡΡΡΡΡΡΡΡΡΩΡΡΡΡ P

PPPPPP PPPPPPPPPPPPP P P qpppppppppppppppppppp pppppppppppppppppppop

Table 3 (Cont'd)

PPPPPPPPPPPPPPPPPPPPP

PPPPPPPPPO PPPPPOOOPPP

PPPPP PPPPPPPPPPPPPPPP

PPPPPPPPPPPPPPPPPPPPP

PPPPPPPPPPPPPPPPPPPP P m

oms C\J P o - tuε xs 0 c W 3 •Η O α< ε1 ο Μ Ο Η

c— cocrvOrHPjrn-=rmvot--cocr\Or-HCMon-=rmm ΗιΗι—ΙΗιΗτΗγΗι—ti—(r—ICMCMCMCUCMCMCM 86

I I I I I I I I I I I I I I I I I I < I

I I I I I I I I I I I I I I I I I I I I

Cont · d

PPPPPPP PPPPPPPPPPPPP I

ppppppp PPPPPPPPPPPPP

PPPPPPP PPPPPPPPPQPPQ

PPPPPPP PPPPPPPPPPPPP

Table 3 (Cont’d)

PPPPPPP PPPPPPPPPPPPP

PPPPPPP PP PPPPPPPPPPP

P P PPPPP PPPPPPPPPPPPO

PPPPPPP PPPPPPPPPPPPP

LTV

o OJ

o ----- - C- 00 CT\ Ο H OJ ^ cvj c\j c\j oo m on • Φ E Ό 0 c w 3 •Η O - = - = - - P < E 1 o Η O H

P o ----- - cn h c\j m -=r in md m u Φ E Ό 0 c CO 3 •Η O = = = = =

P

P E 1 o

Η O H

t— CO CT\ Ο H OJ OO

i—I i—I f—I i I - 87 - LV 10023

I I I I I I I I I I I I I I I I I I I I

PPPPPPPPPPPPPPPPPPPP

PPPPPPPPPPPPP PPPPPPP

PPPPPPPPPPPPPPPPPPPP

Table 3 (Cont'd)

PPPPPPPPPPPPPPPPPPPP

PPPPPPOOOOPPPPPPPOPP

PPPPPPOPPOPPP PPPPOPP

PPPPPPPPPPPPPPPPPPPP

PPPPPPPPPPPPP PPPPPPP

Ln= = = = = = = = = = = = = = = = = = = o-------------------- •=rinvO[^-COCr\Or-(CvJOO-^-UPvUDO-COCr\OiHCMOn i)HriHHHHOJWWCMWN(M CM W CM fH OO Π ΓΠ

(U ε ό 0 e

cn D •HO= = = = = = = = = = = = = = = = = = =

P ra e 1 o

Η O M - 88 - 1 Tēst Example 2

Protective activity on brown leaf spot of peanut (Cercospora arachidicola)

Sandy loam was filled in a 150-ml plastic pot, 5 and peanut (var.: Hanritsusei) was sowed at a rāte. of 1 seed/pot and cultivated for 12 days in an air-conditioned greenhouse (25° to 30°C) to obtain young seedlings in a third true leaf stage. At that time, the aaueous dilute liquor of the emulsifiable concentrate 10 of each tēst compound was sprayed on the foliage at a rāte of 10 ml/pot. After air-drying, the young seedlings were inoculated with Cercospora arachidicola, covered with a polyvinyl chloride film for keeping humidity and placed in an air-conditioned_greenhouse ķept at 25° 15 to 30°C. The seedling were cultivated for further 10 days in the greenhouse in order to sufficiently infect them, and the disease appearance of the leaves was observed. The disease severity was calculated as follows: The leaves were measured for a percentage 20 of infected area and classified into the corresponding disease indices, 0, 0.5> 1, 2, 4; and the disease severity was calculated according to the following equation. - 89 - LV 10023

Disease index

Disease appearance 0 No colony nor infected area on leaf surface 0.5 Colony or infected area of less than 5 % on leaf surface 1 Colony or infected area of less than 20 % on leaf surface . 2 Colony or infected area of less than 50 % on leaf surface 4 Colony or infected area of not less than 50 % on leaf surface

Disease severity (%) Z(Diseas inaex) x (number of leaves) -:- x 100 4 x (Total number of leaves examined) 1 The control of disease was then calculated according to the following equation.

Control of disease (% (Disease severity in treatea plot) 100--x 100 (Disease severity in untreated plot)

As a resultj it was found from Table 4 that the I-A isomer of the compounds of the present invention has 5 a remarkably high protective activity as compared with its I-B isomer. - 90 -

Table 4

- Cont'd - 91 LV 10023

Table 4 (Cont’d)

1 Tēst Example 3

Protective activity on gray mold of cucumber (Botrytis cinerea)

Sandy loam was filled in a 150-ml plastic pot, 5 and cucumber (var.: Sagami-hanjiro) was sowed at a rāte of 3 seed/pot and cultivated for 8 days in a greenhouse to obtain young seedlings in a cotyledonous stage.

At that time, the aaueous dilute liquor of the emulsi-fiable concentrate of each tēst compound was sprayed on 10 the foliage at a rāte of 10 ml/pot. After air-drying, the young seedlings were inoculated with Botrytis cinerea and placed in a humid, constant temperature chamber ķept at 20°C. After 3 days, the disease appearance of the - 92 - 1 cotyledon was observed. The examination of infection and calculation of the control of disease were carried out in the same manner as in Tēst Example 2.

As a result3 it was found from Table 5 that the 5 I-A isomer of Compound 1 has a remarkabiy high protective activity as compared with its Ϊ-Β isomer.

Table 5

Compound Concentration of active ingredient (ppm) Control of disease (*) I-A isomer of Compound 1 500 100 I-B isomer of Compound 1 tt 10 CONHC ;.Hn (1) ļ ^ 9 O^N^NHCO00H3 1! 90

Note: (1) Commercial fungicide - 93 - LV 10023 1 Tēst Example 4

Protective activity on leaf rust of wheat (Puccinia recondita) (curative effect) (young s'eedling tēst)

Sandy loam was filled in a 150-ml plastic pot, 5 and wheat (var.: Noriņ No. 6l) was sowed at a rāte of 10 to 15 seed/pot and cultivated for 7 days in an air-conditioned greenhouse (18° to 23°C) to obtain young seedlings in a first true leaf stage. The seedlings were th'en inoculated with Puccinia recondita and infected 10 by placing them for 16 hours in a humid chamber ķept at 23°C. At that time3 the aqueous dilute liquor of the emulsifiable concentrate of each tēst compound was sprayed thereon at a rāte of 10 ml/pot. The seedlings were cultivated for 10 days in a constant 15 temperature room (23°C) under a fluorescent light, and then the disease appearance of the first true leaf was observed. The examination of infection and calculation of the control of disease were carried out in the same manner as in Tēst Example 2. 20 As a result, it was found from Table 6 that the I-A isomer of the present compounds had a clearly high protective activity as compared with not only its I-B isomer but also the commercial fungicide and the well-known compound. - 94 -

Table

Cont' d - 95 - LV 10023 f

Table 6 (Cont’d) m O O o O o o o o o o o o o O o i—l O o OJ o o o o o H i—! rH i—1 rH rH rH σ\ VO o o o LT\ o in o o o LO o -=r o CM co m o \Ω o ΟΛ o o o in o vo o m i—1 rH i—1 rH rH rH rH o co o o o O o o o o o o o o o o o t- o o o O o o o o o o o o o o r-H 1—I i—l rH 1—1 1—1 1—l I—l rH rH rH rH 1—! rH rH < I CQ < I P3 < PQ < CQ < CQ < CQ < CQ < CQ H H H H H H H H H H H H H H 1—i H r* \o C*- o\ o (—l CM m (M CM CM CM oo cn oo

Cont * d 96

Table 6 (Cont1d) ko o KO o O o . o o m CT\ m o o O m o m o m σ\ O o ko in un i—1 rH o o o o o oo KO -=r o o o o o σ\ ln VO i—i r—ļ rH i—! i—1 -.',έ i—1 OJ * * (U < CQ < CQ < CQ O I 1 1 I 1 c H H H H H H (D oo U m rs 0) on on 2 <D 2 o U o o Ol o 1 to 1 2 X cti o — o o — o 2 c ' /=-^ Hh / ļ 1 ^ 2 ' i 3 O — 2 0—2 o 1 ^2=^ ™ \~—1 2 '2 — α ε O O ο ο Λ c s ο c v V ko id i—1 I—1 oo m cn 1 o o 1—1 rH 0) 15

Cont1 d 97 LV 10023

Table 6 (Cont'd)

Cont 'd » 98

Table 6 (Cont'd)

σ\ ι—I VO =Γ· voon rH

voCM

a03C

CO CM mcn

CM CM O O I—Ivo CM

o σνco OT invo CM 2Φco O I—1 o CO •H 22C3 O aε o ocd Φ2 •H O •HbO C3 <M i—!cd•H O UΦ o o φ -P o 2 • cn O ^r 2 co 40 C Φ 40cd a 3cd Ē 3 0) o Ό2 c Φ 40 3 a 3 .3

O2 40 3 ω 40cd (U3cdε 3Φ O O2 (H in rovoco o O2 403 Φ 40cd a -=T CM CM 44Γ vo O2 'co φ 23•HΌ <D CO O i—I oco •H223 3 O as o o CM * ΦC3 2<D CO O i—I CJ co •H 2 233 O aε o o co * CO 0) C •H2Φ CO ό ι—I oco •rļ2233 O aε o o co 2 c •H2Φco O I—I oco •H 2 2 33 O aε o o a CQ c 2Φco O iH O CO •HΌ233 O aε o o LO * vo * - 99 - LV 10023 1 Tēst Example 5

Protective activity on stem rust of wheat (Puccinia graminis) (curative effect) (young seedling tēst)

Young seedlings of wheat (var.: Noriņ No. 6l) 5 were -obtained in the same manner as in Tēst Example 4.

The seedlings were then inoculated with Puccinia graminis and infected by placing them for 16 hours in a humid chamber ķept at 23°C. At that time3 the acueous dilute liquor of the emulsifiable concentrate of each 10 tēst compound was sprayed thereon at a rāte of 10 ml/pot. The seedlings were cultivated for 10 days in an air-conditioned greenhouse ķept at 23°C, and then the disease appearance of the first true leaf was observed. The examination of infection_and calculation of the 15 control of disease were carried out in the same manner as in Tēst Example 2.

As a result, it was found from Table 7 that the I-A isomer of the present compounds has a clearly high protective activity as compared with not only its I-B 20 isomer but also the commercial fungicide and the well-known compound. 100

Table 7

- Cont'd - 101 LV 10023 30 Table 7 (Cont I-A •d) 100 20 5 100 100 100 I-B • 50 80 31 I-A 100 20 5 100 100 100 I-B 50 0 32 I-A 100 20 5 100 100 100 I-B 50. 0 Well-known compound as a reference 0 Cl-^ ^-0 - CH - C - C(CH3_)3 ", 1 u u-N 100 20 5 84 13 0 0 Cl-^ ^-CH2CH - CH - C(CH3)3 ^ N\ N 1 «2 100 20 5 87 18 0 0 ί - ""Ο 1 53 u- N 50 0

Note: *1 Commercial fungicide, a compound disclosed in B.P. No. 1364619. *2 Compound disclosed in West German Patent No. 2734426. *3 Compound disclosed in U.S. Patent No. 4086351 - 102 1 Tēst Exaraple 6

Protective activity on powdery mildew of barley (Erysiphe graminis) by foliar application (young seedling tēst) 5 Sandy loam was filled.in a 150-ml plastic • pot, and barley (var.: Goseshikoku) was soyred at a rāte of 10 - 15 šeed/pot and cultivated for 7 days in an air-conditioned greenhouse (l8° to 23°C)"to obtain young seedlings in a first true leaf stage. Thereafter, the 10 aqueous dilute liquor of the emulsifiable concentrate of each tēst compound was sprayed on the foliage at a rāte of 10 ml/pot. After air-drying, the young seedlings were inoculatea with Erysiphe graminis and cultivated for 10 days in a constant temperature room (23°C) under 15 a fluorescent light. The disease appearance of the first true leaf was then observed. The disease severity was calculated as follows: The leaves were measured for a percentage of infected area and classified into the corresponding disease inaices, 0, 0.5, 1, 2, 4; and the 20 disease severity was calculated according to the following eauation. - 103 - LV 10023

Disease index 0 0.5 1 2 4

Disease appearance No colony. on leaf surface Colony of less than 5 % on leaf surface Colony of less than 20 % on leaf surface Colony of less than 50 % on leaf surface Colony of not less than 50 % on leaf surface

Disease severity (%) Σ(Disease ināex) x (number of leaves) -- x 100 4 x (Total number of leaves examined) 1 The control of disease was then calculated according to the following equation.

Control of 1nn disease {%) (Disease severity in treated Dlot) . - x 100 (Disease severity in untreated plot)

As a result, it was found from Table 8 that the present compounds have an excellent protective 5 activity against powdery mildew of barley, and that the activity is equal or superior to that of the reference compound. - 104 -

Table 8 Tēst compound Concentra-tion of active in gredient (ppm) Control of disease (%) Compound No. Klnd of geometrical isomer 1 I-A isomer 500 100 2 tt 11 3 t! 11 11 4 tt 5 11 tt tt 6 11 11 It 7 11 !t tt 8 11 īī īī 9 11 11 10 11 11 11 11 11 tt 12 1! _ 11 11 13 11 11 11 i4 11 11 11 15 11 11 11 16 11 11 tt 17 11 11 11 18 11 īl It 19 11 π tt 20 11 11 11 21 11 11 11 22 11 11 11 23 11 11 11 24 tl 11 25 11 11 11 26 11 11 27 11 It 11 28 11 11 11 29 11 11

Cont'd 105 LV 10023

Table 8 (Cont’d) 30 I-A isomer 200 100 31 11 1! 11 32 11 11 11 33 tl 11 II 34 11 11 11 35 1t 50 Tl 36 11 II 11 37 11 11 11 38 11 11 11 39 11 11 11 40 11 II 90 41 II tl 91 42 . 11 11 89 43 11 11 93 44 īī 11 100 45 11 11 11 46 11 11 . 95 47 11 11 100 48 It 95 49 tl tt 100 50 II II 80 51 II īī 100 52 II 11 II 1 I-B isomer 500 11 2 11 II 11 3 1! 11 11 4 11 II 11 5 11 11 11 6 11 11 11 7 11 II 11 8 11 11 11 9 11 II 11 10 IT II 11 - Cont'.d - - 106 -

Table 8 (Cont’ d) 11 I-B isomer 50 c 13 11 tt 14 II tt 15 II It 16 tt tt 17 tt tt 18 II 1! 19 11 tt 20 tt tt 21 tt tt 22 tl It 23 It II 24 tl tt 25 tl tt 26 tt ĪI 27 II l! 28 ĪI _ tr 29 I! tt 30 tl 11 31 ĪI ĪI 32 It II 33 tl tt 34 tt II 35 tt tt 36 tt tt 38 tt tt 39 11 tl 43 II 11 47 tt II 51 tl 11 1' II-A isomer tt 2' II II 3' lī tt 4' tl tt 100

It Π 11

TT

II I! tl

II tt

It

II

II Π

It

II

It

II tf

II

Cont'd 107 LV 10023

Table 8 (Cont'd) 5' II-A isomer 6’ " γ t i! 8’ · " g i ii 101 ii 11' " 121 I. 13’ "

141 II 15' " 16 ’ " 17' " 18' » 191 " 2o i ir 21' " ~ 22' " 23' " 241 ii 25' " 26' " 27’ " 28' 29' " 30' " 31'. " 32' 33' 1’ II-B isomer

2 I II

2 I II lļ i ii 500 100 u 11 IT īt 11 It Tt tt It tt M u It tt Π 11 tī i.t. tt tī tt tī tī tī tt tt tt IT tt It ĪI tī II tt tt tt It It tī tt tī tī īt tī tt tt tī tī It tt It tī tī tī tt 11 īt tī tt It tī tt tt

Cont’d - 108

Table 8 (Cont'd) 5’ II-B isomer 500 100 6’ 1! tt īī . 7' f! It īt 8’ īī 9' 11 tī tī 10’ īt tt tī 11' Π tt īī 12' It 11 īī 13’ tī 14' IT tī īī 15' It 11 īī 16' tī īī 17' tī tī tt 18' 1! tī 19' 1! tī II • 20' II II 21' t! — t! īī 22' 11 īt 23' tt īī 24' It tī īī 25' It īī ī! 26' It It 27' tī 28' tī tī 29' īt tt īī 30' It īt īī 31' tī It 1ī 32' 11 īt t! 33' tī tī Reference compound nu 500 100 3 7“ "Λ (Commercial 200 81 0 N - C 1-^27 fungicide) r 50 43 ch3—1— - 109 - LV 10023 1 Tēst Example 7

Five hundred grams of soil mixture comprising sea sand, mountain soil and peat was filled in a flower pot of 13 cm in diameter, and Pot-mum (var.: Snow Ridge) 5 was cultivated therein. Two weeks after setting, the Pot-mum was pinched and cultivated in a 3-stem form, and then new buds grew. Two weeks after pinching, an aqueous dilute liquor containing a pre-determined cencent-ration of each tēst compound was applied to the Pot-mum, 10 and 42 days after the application of pesticide, the plant growth controlling effect was examined. The results are shown in Table 9 ·

The effect was evaluated as follows: An increase in plant height was calculated as a difference between 15 the initial plant height at the time of the application and the plant height on the 42nd day after the application, and expressed in height index with the corresponding difference in the untreated plot as 100. The values in the table are a mean value of three replicationš. 20 As a reference compound, B-Nine (N,N-dimethyl- aminosuccinamic acid) was used. 110

Dwarfing tēst for Pot-mum

Table 9

Compound Concentra-tion of active in-gredient (ppm) Height (56) Maximum' leaf length (56) Flower diame- ter (56) Phyto- toxi- city I-A isomer of Compound 1 500 65 97 98 None I-B isomer of Compound 1 500 ' 81 102 105 n None I-A isomer of Compound 4 . 500 73 100 101 None I-B isomer of Compound 4 500 85 101 102 None I-A isomer of Compound 9 500 67 99 98 None I-B isomer of Compound 9 500 “88 100 i 100 ļ None ! I-A isomer of Compound 11 500 57 95 95 None I-B isomer of Compound 11 500 81 102 100 None I-A isomer of Compound 21 500 73 97 99 None I-B isomer of Compound 21 500 86 97 101 None I-A isomer of Compound 26 500 75 101 100 None I-B isomer of Compound 26 500 88 100 98 None I-A isomer of Compound 30 1000 ' 63 - - None I-A isomer of Compound 31 1000 65 - - None - Cont' d - 111 LV 10023

Table 9 (Cont'd) I-A isomer of Compound 35 500 64 101 98 None I-A isomer of Compound 43 500 62 98 100 None I-B isomer of Compound 35 500 89 102 101 None B-Nine S1 4000 86 98 103 None No treatment - 100 100 100 None *1 Reference compound (commercial fungicide) 0 II /CH3 CH0C - NHN | 2 \ CH0C - 2II 0 OE Cn3 112 1 Tēst Example 8

Herbicidal activity tēst on field weeds

Soil was mixed with the seeds of large crabgrass (Digitaria sanguinalis), redroot pigweēd (Amaranthus 5 retroflexus) and coramon lambsquarter (Chenopodium album) and filled in a 1/5000 are Wagner’s pot. Thereafter, the aqueous dilute liquor of the emulsifiable concentrate containing a pre-determined amount of active ingredient was applied to the surface of the soil by means of a hand 10 sprayer. After the application, sugar beet seed.lings (var.: Monohil) at a 5-leaf stage cultivated in paper pots were transplanted to the Wagner*s pot. Thereafter, the seedlings were cultivated in a greenhouse. Twenty days after the application, the herbicidal activity and 15 phytotoxicity to crops were observed. The results are shown in Table 10. The herbicidal activity was expressed by nume-rals, 0 to 5, as shown below, provided that the phytoto-• xicity to crops was also expressed on the same Standard. 0 Inhibition percentage 0 - 9 % 20 1 " 10 - 29 % 2 " 30 - 49 % 3 " 50 - 69 % ** " 70 - 89 % 5 90 - 100 % 25 As apparent from Table 10, the I-A isomer of the present compounds showed a far strong herbicidal activity as compared with the I-B isomer. - 113 - 83001. ΛΊ

Table 10 Compound Dosage (g/a) Herbicidal ac.tivity Phytoto-xicity to sugar beet Large crab- grass Redroot pigweed Common lambs- quarter I-A isomer of 40 5 5 5 0 Compound 1 20 4 5 5 0 I-B isomer of 40 3 4 4 0 Compound 1 20 2 3 3 0 I-A isomer of 40 .4 5 5 0 Compound 2 20 4 4 5 0 I-B isomer of 40 3 3 3 0 Compound 2 20 1 3 3 0 I-A isomer of 40 5 5 5 0 Compound 3 20 4 5 5 0 I-B isomer of 40 3 3 3 0 Compound 3 20 2 3 3 0 I-A isomer of 40 5 5 5 0 Compound 4 20 4 5 5 0 I-B isomer of 40 3 3 3 0 Compound 4 20 1 2 3 0 I-A isomer of 40 4 5 5 0 Compound 5 20 4 4 5 0 I-B isomer of 40 2 2 3 0 Compound 5 20 2 2 1 0 I-A isomer of 160 4 5 5 0 Compound 6 80 4 . 5 5 0 I-B isomer of 160 2 3 2 0 Compound 6 80 1 1 2 0 I-A isomer of 40 5 5 5 0 Compound 7 20 4 4 5 0 I-B isomer of 40 3 3 3 0 Compound 7 20 2 3 3 0 - Cont’d - - 114 -

I

Table 10 (Cont'd) I-A isomer of 4o 4 5 · 5 0 Compound 8 20 4 4 4 0 I-B isomer of 40 2 3 4 0 Compound 8 20 1 2 3 0 I-A isomer of 40 5 5 5 0 Compound 9 20 4 5 5 0 I-B isomer of 40 2 3 3 0 Compound 9 20 2 1 3 0 I-A isomer of 40 5 4 5 0 Compound 10 20 4 4 4 0 I-B isomer of 40 2 3 3 0 Compound 10 20 2 2 3 0 I-A isomer of 40 5 5 5 0 Compound 11 20 4 5 5 0 I-B isomer of 40 3 4 4 0 Compound 11 20 3 2 2 0 I-A isomer of 160 4 ~ 4 4 0 Compound 12 80 4 4 4 0 I-A isomer of 160 4 5 5 0 Compound 13 80 4 4 5 0 I-B isomer of 160 2 4 3 0 Compound 13 80 1 1 2 0 I-A isomer of 80 4 5 5 0 Compound 14 40 4 5 5 0 I-B isomer of 80 3 4 3 0 Compound 14 40 2 3 3 0 I-A isomer of 40 5 5 5 0 Compound 15 20 4 4 4 0 I-B isomer of 4o 3 4 3 0 Compound 15 20 3 3 2 0 I-A isomer of 80 5 5 5 0 Compound 16 40 4 5 5 0 - Cont'd - 115 LV 10023

Table 10 (Cont'd) I-B isomer of 80 1 3 3 0 Compound 16 4o 0 3 3 0 I-A.isomer of 40 • 5 5 5 0 Compound 17 20 4 4 5 0 I-B isomer of 40 1 2 2 0 Compound 17 20 0 1 2 0 I-A isomer of 80 4 5 4 0 Compound 18 40 4 4 4 0 I-B isomer of 80 0 1 2 0 Compound 18 40 0 1 1 0 I-A isomer of 8o 5 5 5 0 Compound 19 4o 4 5 5 0 I-B isomer of 80 3 3 3 0 Compound 19 40 2 1 3 0 I-A isomer of 160 4 5 5 0 Compound 20 80 Iļ 4 4 0 I-B isomer of 160 2- 4 3 0 Compound 20 8o 0 2 1 0 I-A isomer of 160 5 5 5 0 Compound 21 8o iļ 5 5 0 I-B isomer of 160 3 3 2' o“ Compound 21 80 2 1 2 0 I-A isomer of 160 4 4 4 0 Compound 22 8o 4 4 4 0 I-B isomer of 160 2 4 3 0 Compound 22 80 1 1 2 0 I-A isomer of 80 4 5 5 0 Compound 23 40 4 5 5 0 I-B isomer of 80 2 2 2 0 Compound 23 40 0 1 2 0 I-A isomer of 80 4 4 5 0 Compound 24 4o 4 4 4 0 I-A isomer of 16o 5 5 5 0 Compound 25 80 4 5 4 0 1 - Cont'd - - 116 -

Table 10 (Cont’d) I-B isomer of 160 2 *1 3 0 Compound 25 80 0 2 3 0 I-A isomer of *10 5 5 5 0 Compound 26 20 *1 5 5 0 I-A isomer of *10 5 5 5 0 Compound 27 20 *1 5 5 0 I-A isomer of *10 5 5 5 0 Compound 35 20 5 5 5 · 0 I-A isomer of 80 5 5 5 0 Compound 36 *10 *1 *1 . 5 0 I-A isomer- of 160 5 5 5 0 Compound 37 80 ķ 5 5 0 I-A isomer of 80 5 5 5 0 Compound 38 *10 *1 *1 *( 0 I-A isomer of 80 *1 5 5 0 Compound 39 *10 *1 5 5 0 I-A.isomer of *10 5 5 5 0 Compound *10 20 - *1 5 *1 0 I-A isomer of 80 5 5 5 0 Compound *11 *10 5 h *1 0 I-A isomer of *10 *1 5 5 0 Compound *12 20 *1 *1 5 0 I-A isomer of 80 5 5 5 0 Compound *13 *10 5 5 5 0 I-A isomer of 80 5 5 5 0 Compound *1*1 *10 *1 5 5 0 I-A isomer of 160 5 5 5 0 Compound *15 80 *1 5 5 0 I-A isomer of. 160 *1 5 5 0 Compound *16 80 *1 5 *1 0 I-A isomer of 80 5 5 . 5· 0 Compound *17 *10 5 5 5 0 1 1 - Cont'd - - 117 - LV 10023

Table 10 (Cont'd) I-A isomer of 16o 4 5 · 5 0 Compound 48 80 4 5 5 0 I-A isomer of 160 4 5 4 0 Compound 49 80 4 4 4 0 I-A isomer of 80 5 5 5 0 Compound 50 40 4 5 5 0 I-B isomer of 4o 2 3 3 0 Compound 35 20 1 2 2 o ; I-B isomer of 80 3 3 3 0 Compound 43 40 2 3 1 0 1 Tēst Example 9

Height-controlling effect on soybean and barley

Sandy loam v/as filled in a 500-ml plastic pot. The soil in the upper half of the pot was taken out, well 5 mixed with 10 ml of the aaueous dilute liquor of the emulsifiable concentrate of each tēst compound and returned back to the pot. Thereafter, soybean and barley were sowed in the treated soil at rātes of 3 seeds/pot and 5 seeds/pot, respectively. 10 · The soybean and barley were cultivated in a glass house ķept at 25°C, and after 14 days, the height of each plant was measured. The results are shown in Table 11. The numerical values in the table mean the average height of two soybeans and that of three barleys 15 whichrwere expressed in percentage with the corresponding average height in the untreated plot as 100.

As a result, it was found that the I-A isomer - 118 - 1 of the present corapounds displays a remarkably strong height-controlling effect as compared with the I-B isomer v;hich is a reference compound. Further, with any of the I-A and the I-B isomers, no phytotoxicity such 5 as chlorosis and necrosis was observed, and it was found that the leaves became rather deep green.

Table 11 Tēst compound Dosage rāte (g/a) Soybean (*> — Barley (*) I-A isomer of Compound 1 10 18 17 5 22 18 2.5 37 26 I-B. isomer of Compound 1 10- 22 52 5 28 47 2.5 46 89 I-A isomer of Compound 35 10 ļ 20 70 5 33 88 2.5 54 95 I-A isomer of Compound 40 10 21 57 5 28 78 2.5 47 102 I-A isomer of .Compound 43 10 19 76 5 24 100 2.5 50 102 - Cont'd - 119 - LV 10023

Table 11 (Cont’d) I-A isomer of Compound 47 10 •33 89 5 45 98 2.5 72 97 I-A isomer of Compound 50 10 44 77 5 65 OO ko 2.5 97 98 . I-B isomer of Compound 35 10 85 98 5 93 102 2·5 .. 99 100 1 Tēst Example 10

Controlling effect on the growth of internode of barley Barley (var.: C-oseshikoku) was sowed in field on November 20th, and the next year the aaueous dllute 5 liauor of. the emulsiflable concentrate of the I-A isomer of Compound 1 was sprayed on the foliage once (on April 4th) and twice (on April 4th and 24th).

The barley in each plot was reaped on May 28th, and the length of internode of 30 barley straws per 10 plot was measured. As shovm in Table 12, the length of, chiefly, the fourth and fifth internodes in the treated plot was outstandingly shortened as compared with the untreated plot, and besides the total length of the straw in the treated plot was also shortened. 15 Phytotoxicity such as yellowing and sterility was never observed. 120

Table 12 χ Η -P *=Γ =Τ CM ιη «5 bO ε • # • ρ C υ νο -Γ Ο CO Ο 1) —' ο ο Ο σ\ Ε-ι Η Η ι—1 (Η χ ε ιη -=Γ ί—i Ρ CJ • « • * ί>- ^ νο ιη ιη νο ✓"Ν χ ε ιη c— οο ι—1 Ρ ο * • • • νο ^ σ\ οο νο 0- =τ CM νο -=Γ χ ε • . • • • -Ρ ο rH ον νο C— ιη ^ ι—1 C- ο ο CM λ ε * • • • ρ υ οο CVJ ο σ\ -ΞΓ ^ γΗ γΗ γΗ f- ο- ο CO ό ε • • • · ?-< ο ιη •ΞΓ m CM οο w γΗ ι—I rH ι—I ιη rH c— ι—i σ ε • • . . C Ο c^- σ\ ο ον CM ^ ι—i ι—1 C\J t—I 1 rH ο CM CO D D ε • • • • Ρ Ρ Ό Ο OJ ιη νο νο tQ C 0 ^ γΗ *Η C ΟΟ οο οο ~η 1 ε ε ε Ρ ο. Φ a Ο. Φ Φ Ρ Ο4 Ο a φ a ο φ c 1 •Η ο *Η φ ιη ^ Ο C Ο £ &η ε 0U Ρ ιη ο ιη ρ «Η Ο Ό ι—1 C 1 φ 3 Ρ ε ό ο nJ ο C ρ α ω ω Ο “ η m ε U •Η Ο φ ο Ρ Ρ α ΕΗ ο C < ε ο φ ι ο 2 ε Η Ο 121 LV 10023 1 Tēst Example 11

Growth controlling effect on turf S'oil mixture, a 3:1 mixture of mountain soil and peat, was filled in a 1/5,000 are Wagner's pot, and Korai .:5 lawn grass (Zoysia matrella L) was transplanted thereto on December 6th.

The lawn grass was cultivated in a greenhouse ķept at 30°C with repeated fertilization' and lawn mowing3 until the growth of lawn grass became uniform. Immediately 10 after lawn mowing on May 9th, the aqueous dilute liquor of the emulsifiable concentrate of each tēst compound wās applied at a rāte of 10 ml/pot by means of a hand sprayer.

On June 2nd3 an increase in the height of lawn grass was measured to evaluate the growth controlling 15 effect of the tēst compound. The effect was expressed in height index with the corresponding increase in the untreated plot as 100. The results are shovrn in Table 13. It is apparent from the table that the compounds of the present invention have a growth controlling effect on 20 lawn grass.

Table 13 Tēst compound Dosage rāte (g/a) Height index (%) I-A isomer of Compound 1 20 71 T-A isomer of Compound 27 20 74 I-B isomer of Compound 1 20 86 ’No treatment - 100 (7.0 cm) 122 1 Tēst Example 12

Herbicidal activity tēst on paddy field weeds

Wagner's pots (1/5,000 are) wēre eaeh filled with 1.5 kg of paddy field soil and ķept under a flooded 5 condition. Rice seedlinģs in a three-leaf stage were transplanted thereto, and the seeds of barnyard grass (Echinochloa crus-galli) and Bulrush sp. (Scirpus .juncoides var. Hotarui Ohwi) were sowed therein. Thereafter, a required amount of each tēst compound 10 was applied to the soil in a flooded condition.

Twenty-five days after the application, the herbicidal activity of the tēst compound was examined on the sowed weeds as well as broad-leaved weeds and slender spikerush (Eleocharis acicularis) which emerged 15 spontaneously.' The results are shown in Table 14.

In applying the tēst compounds, a pre-determined amount of each compound was formulated into a wettable powder and applied at a rāte of 10 cc/pot by means of a pipette. The herbicidal activity was expressed in numerals ranging from 0 to 5. 0 Inhibition percentage 0 - 9 % 1 11 10 - 29 % • 2 11 30 - 49 % 3 11 50 - 69 % 4 It 70 89 % 5 It ,90 - 100 % Ali the tēst compounds did i not show phytotoxicity to rice plants, for example malformation, yellowing and chlorosis. - 123 - LV 10023

Table 14

Dosage Herbicidal activity Tēst compound rāte Barn- Broad- Bulrush Slender (g/a) yard leaved sp. spikerush grass weed I-A isomer of 20 5 5 5 , r Compound 1 10 5 5 5 - I-A isomer of 20 5 5 5 Compound 3 10 4 5 4 - I-A isomer of 20 5 5 5 Compound 4 10 4 5 4 - I-A isomer of 20 5 5 5 _ Compound 2 10 5 5 5 - I-A isomer of 20 5 5 5 Compound 27 10 5 5 4 - I-A isomer of 20 5 5 5 Compound 5 10 4 5 . 5 - I-A isomer of 20 5 5 5 Compound 9 10 5 5 5 - I-B isomer of 20 3 3 3 Compound 1 10 2 3 2 - I-A isomer of 40 r cr Compound 30 b b b I-B isomer of 4o r c: Compound 30 b b b I-A isomer of 40 C c £T Compound 31 b b b I-B isomer of 40 c CT £7 Compound 31 D b b Ī-A isomer of 4o 5 5 Compound 32 b I-B isomer of r 40 c Compound 32 D b b - Cont'd - 124 i

Table 14 (Cont'd). I-A isomer of Compound 33 40 1 5 5 1 5 I-B isomer of Compound 33 40 5 5 - 5 I-A isomer o.f Compound 34 40 5 5 - 5 I-B isomer of Compound 3^ 40 5 5 - 5 1 Tēst Example 13

Protective activity tēst on sheath blight of rice (Rhizoctonla solani)

The aaueous dilute_ļiquor of the emulsifiable 5 čoncentrate of each tēst compound was sprayed on potted rice plants (var.: Kinki No. 33) cultivated in a greenhouse for about 2 months. After air-drying3 the leaf sheath of rice stems was inoculated by sticking the mycelial disc (diameter 5 cm) of Rhizoctonia solani. 10 After inoculation, the rice plants were infected in a humid chamber (28°C) for 4 days3 and the disease appearance was examined.

The disease severity was calculated as follows: The leaf.sheath was measured for a percentage of infected 15 area and classified into the corresponding disease indices, 0, 1, 2, 4, 8; and the disease severity was calculated according to the following equation. - 125 - LV 10023

Disease····1 index

Disease appearance 0 No infected area and no growt.h of colony 1 No infected area but slight growth of colony 2 Infected area of less than 0.5 cm i} Infected area of 0.5 - 2 cm 8 Infected area of more than 2 cm

Disease severity Σ(Disease (number of leaf index) sheaths) -:- χ ioo 8 x (Total number of leaf sheaths examined) 1 The control of disease was then calculated according to the follovring equation.

Control of disease ($») = 100 - (Disease severity in treated plot) - x ioo (Disease severity in untreated plot)

As shown in Table 15, it was found that the I-A isomer of the present compounds has a remarkably high 5 protective activity as compared vrith the I-B isomer, and that the activity is equal or superior to that of the reference compound. - 126 -

Table· 15 Tēst compound Concentration of active ingredient (ppm) Control of disease (%) I-A isomer of Compound 38 500 95 I-A isomer of Compound ff 95 I-A isomer of Compound 45 Tt 95 I-A isomer of Compound 46 11 80 Ι-Ά—isDmer of Compound 47 11 100 (Reference compound) I-B isomer of Compound 38 11 0 I-B isomer of Compound 43 11 0 I-B isomer of Compound 47 11 0 Validamycin S1 30 78 S1 Reference compound (commercial fungicide) 1 Preparation Example 1 Dust

One part of the I-A isomer of each of the present compounds (1) to (52), 89 parts of clay and 10 parts of talc are well mixed while being powdered to 5 obtain a dust contalning 1 % of active ingredient.

Preparation Example 2 Dust

Three parts of the I-A isomer of' each of the present compounds (1) to (52), 67 parts of clay and 30 parts of talc are well mixed while being powdered to - 127 - LV 10023 1 obtain a dust containing 3 % of active ingredient.

Preparation Example 3 Wettable powder

Thirty parts of the I-A isomer of each of the present compounds (1) to (52), ^5 parts of diatomaceous 5 earth, 20 parts of white carbon, 3 parts of a wetting aģent (sodium laurylsulfate) and 2 parts of a dispersing aģent (calcium lignosulfonate) are well mixed while being powdered to obtain a wettable powder containing 30 % of active ingredient. 10 Preparation Example k V/ettable powder

Fifty parts of the I-A isomer of each of the present compounds (1) to (52)_, ^5 parts of diatomaceous earth, 2.5 parts of a vretting aģent (calcium alkyl-benzenesulfonate) and 2.5 parts of a dispersing aģent 15 (calcium lignosulfonate) are v/ell mixed while being powdered to obtain a wettable povrder containing 50 % of active ingredient.

Preparation Example 5 Emulsifiable concentrate

Ten parts of the I-A isomer of each of the 20 present compounds (1) to (52), 8o parts of cyclohexanone and 10 parts of an emulsifier (polyoxyethylene alkylaryl ether) are mixed to obtain an emulsifiable concentrate containing 10 % of active ingredient. - 128 - 1 Preparation Ēxample 6 Granulē

Pive parts by weight of the I-A isomer of each of the present compounds (1) to (52), 40 parts by weight of bentonite, 50 parts by weight of clay and 5 5 parts by weight of sodium lignosulfonate are well mixed while being powdered. The mixture is well kneaded with water, granulated and dried to obtain a granule.

Preparation Example 7 Dust

Two parts of the II-A isomer of each of the 10 present compounds (11) to (33'), 88 parts of clay and 10 parts of talc are well mixed while being powdered' to obtain a dust containing 2 jž of active ingredient.

Preparation Example 8 Dust

Three parts of the II-A isomer of each of the 15 present compound (1') to (331)> 67 parts of clay and 30 parts of talc are vrell mixed while being powdered to obtain a dust containing 3 % of active ingredient.

Preparation Example 9 Wettable powder

Thirty parts of the II-A isomer of each of the 20 present compounds (1') to (33*), ^5 parts of diatomaceous earth, 20 parts of white carbon,· 3 parts of a wetting aģent (sodium laurylsulfate) and 2 parts of a dispersing aģent (calcium lignosulfonate) are well mixed while being powdered to obtain a wettable powder containing 25 30 % of active ingredient. - 129 - LV 10023 1 Preparation Example 10 Wettable powder

Pifty parts of the II-A isomer of each of the present compounds (1') to (33'), ^5 parts of diatomaceous earth, 2.5 parts of a wetting aģent (calcium alkylbenzene-5 sulfonate) and 2.5 parts of a disperšing aģent (calcium lignosulfonate) are well mixed while being powdered to obtain a vrettable powder contianing 50 % of active ingredient.

Preparation Example 11 Emulsifiable concentrate 10 Ten parts of the II-A isomer of each of the .present compounds (1') to (33'), 80 parts of cyclohexanone and 10 parts of an emulsifier (polyoxyethylene alkylaryl ether) are mixed to_obtain an emulsifiable . concentrate containing 10 % of active ingredient. 15 Preparation Example 12 Granule

Five parts by weight of the II-A isomer of each of the present compounds (1') to (33'), ^0 parts by weight of bentonite, 50 parts by weight of clay and 5 parts by weight of sodium lignosulfonate are well mixed 20 while being powdered. The mixture is well kneaded with water, granulated and dried to obtain a granule containing 5 % of active ingredient.

Preparation Example 13 Wettable powder

Eighty parts of the I-A isomer of each of the 25 present compounds (1) to (52), 15 parts of diatomaceous - 130 - 1 earth, 2.5 parts of a wetting aģent (calcium alkyl-benzenesulfonate) and 2.5 parts of a dispersing aģent (calcium lignosulfonate) are well mixed while being powdered to obtain a wettable powder containing 80 % 5 of active ingredient. 1 "51 LV 10023 WHAT IS CLAIMED IS: 1. A geometrical isomer of the formula

OR

CH = C - CH - R 1

wherein R^ is a hydrogen atom, a C^—C^ alkyl, Cσμ alkenyl or 2-propynyl group, R2 is a C^-Cg alkyl, cyclo-propyl or l-methylcyclopropyl group, R^, which may be the same or different, is a halogen atom, a C^-C^ alkyl, halogen-substituted C^-C^ alkyl, alkoxy, phenoxy, phenyl, cyano or nitro group, and n is an integer of 0 to 3j obtained by reducing-one of the two geometrical isomers of a triazole compound represented by the formula, 0

wherein R2> R^ and n are as defined above, of which the olefin proton appears at a higher magnetic field on the NMR spectrum in deutero chloroform, or by further etherifying the resulting reduced product, or its salts. 2. A geometrical isomer or its salts according to

Claim 1, wherein R^ is a hydrogen atom and R2 is a tert-butyl group. - 132 - 3. A geometrical isomer or its salts according to

Claim 2, vrherein n is 1 and R^ is a chlorine atom at the 4-position. *t. A geometrical isomer or its salts according to

Claim 2, wherein n is 2 and is chlorine atoms at the 2- and 4-positioņs. 5. A geometrical isomer according to Claim 1, wherein R^ is a hydrogen atom, R2 is a l-methylcyclopropyl group, R^ is a halogen atom and n is 0, 1 or 2. 6. One of the two geometrical isomers of a triazole compound represented by the formula,

vrherein R2, R^ and n are as defined in Claim 1, of which the olefin proton appears at a higher magnetic field on the NMR spectrum in deutero chloroform. 7. One of the two geometrical isomers of a triazole compound represented by the formula, 0

- 133 LV 10023 wherein R2 is a l-methylcyclopropyl group, and and n are as defined in Claim 1, of which the olefin proton āppears at a lower magnetic field on the NMR spectrum in deutero chloroform. 8. A process for preparing one of the two geometri cal isoraers of a triazole compound represented by * the formula, 0

wherein R2, R^ and n are as defined in Claim 1, of which the olefin proton appears at a higher magnetic field on the NMR spectrum in deutero chloroform, characterized by isomerizing the other geometrical isorner of which the olefin proton appears at a lower magnetic field on the NMR spectrum in deutero chloroform, by irradiation with rays. 9* A process for preparing one of the two geometri cal isomers of a traizole compound represented by the formula,

- 134 - vrherein R2, R^ and n are as defined in Claim 1, of which the olefin proton appears at higher magnetic field' on the NMR spectrum in deutero chloroform, characterized by isomerizing a mixture of the two geometrical isomers thereof, by irradiation with rays. 10. A process for preparing a geometrical isomer of the formula,

OH

I CH - R2 wherein R2, R^ and n are as defined in Claim 1, characteriz ed by reducing one of the two- geometrical isomers of a triazol compound represented by the formula,

wherein R2, R^ and n are as defined in Claim 1, of which the olefin proton appears at a higher magnetic field on the NMR spectrum in deutero chloroform. 11. A process for preparing geometrical isomer of the formula, 135 - 1LV 10023

OR

CH = C - CH - R2 vrherein R^ is a C-^—C^ alkyl, C^—Cjļ alkenyl or 2-propynyl group, and R£, R3 and n are as defined.in Claim 1, characterized by reacting a geometrical isomer of the formula,

OH

vrherein R2, R^ and n are as defined in Claim 1, obtainea by reducing one of the two geometrical isomers of a triazole compound representea by the formula, 0

N vrherein R2, R^ and n are as defined in Claim 1, of vrhich the olefin proton appears at a higher magnetic field on the NMR spectrum in deutero chloroform, or its alcoholate vrith a reactive C^-C^ alkyl, C^-C^ alkenyļ or 2-propynyl derivative in the presence of a base, or salts thereof, 12. A fungicide, herbicide and/or plant growth - 136 - regulator for agriculture and horticulture characterized by containing as an active ingredient a geometrical isomer of the formula,

wherein R^, R2, R^ and n are as defined in čiaim 1, obtained by reducing one of the two geometrical isomers of a triazole compound represented by the formula,

wnerein R2, R^ and n are as defined in Claim,1, of which the olefin proton appears at.a higher magnetic field on the NMR spectrum in deutero chloroform, or by further etherifying the resulting reduced product, or salts thereof. 13- A fungicide for agriculture and horticulture characterized by contianing as an active ingredient one of the two geometrical isomers of a triazole compound represented by the formula, - 137 - LV 10023 Ο

wherein ί^, R^ and n are as defined in Claim 1, of which the olefin proton appears at a higher magriefcic field on the NMR spectrum in deutero chloroform, or salts thereof. - 138 -

ABSTRACT OP THE DISCLOSURE

The present invention relates to one of the two geometrical isomers (a compound defined as I-A isomer in the description below) of a triazole compound represented by the formula (I) or (II),

(II) wherein R^ is a hydrogen atom, a Cļ-C^ alkyl, C^-C^ alkenyl or 2-propynyl group, R2 is a C^—Cg alkyl, cyclopropyl or l-methylcyclopropyl group, R^, whlch may be the same or different, is a halogen atom, a Cļ-Cjj alkyl, halogen-substituted C^-C^ alkyl, alkoxy, phenoxy, phenyl, cyano or nltro group, n is an integer of 0 to 3> and the term, halogen, means chlorine, bromine and fluorine atoms, its salts, production thereof and a fungicide, herbicide and/or plant growth regulator for agriculture and horticulture containing said compound as an active ingredient.

Claims

EN 10023 EXAMPLE OF THE INVENTION / I. Geometric isomer of formula

0RT I1 CII-R2 wherein R 1 is hydrogen, C 1-10 alkyl, C 1 -C 4 alkenyl, or 2-pro-pyl, R 2 'is' C 1-6 alkyl, cyclopropyl or 'I' methylcyclo-propyl, R 1, which may be the same or different, is halogen, alkyl, halogen-substituted C 1 -C 6 alkyl, C 1-4 alkoxy, phenoxy, phenyl, cyano, or nitro and n is an integer from 0 to 3, and obtained by reducing one of the two geometric isomers of the triazole compound of the formula:

R 2 2 wherein R g, R j and n are as defined above, wherein the olefin proton appears in a stronger magnetic field of the PMR spectrum (deuterochloroform) or ether via the resulting reducing product or salts thereof. 2. (Geometric isomer or its salts according to claim 1, wherein R 1 is hydrogen and R 1 is tert-butyl. 3. Deometric isomer or its salts according to claim 2, wherein a is I and is a chlorine atom in the 4-position 4. deometric isomer or its salts according to claim 2, wherein a is 2 and R 1 is chlorine in the 2- and 4- position 5. deometric isomer according to patent formula I. a point where R 1 is hydrogen, R 2 is I-methylcyclopropyl, R 1 is halogen, and n is 0, I or 2.

One of the two geometric isomers of the triazole compound, the formula of which is: R, wherein R 2, R j and n are as defined in claim I of the patent formula, wherein the olefin proton appears in a stronger magnetic field of the PMR spectrum (deuterohloroform).

7. One of the two geometric isomers of the triazole compound having the formula: 0

R II c 2 3 EN 10023 wherein Rg is I-methylcyclopropyl, in and n is as defined in claim I of the patent formula, wherein the olefin proton appears in the weakest magnetic field of the PMR spectrum (deuterohloroform).

A process for obtaining one of two geometric isomers of a triazole compound having the formula: wherein: Rg, Rj and n are as defined in claim 1 of the patent formula The olefin proton appears in the strongest magnetic field of the PMR spectrum (deiterohlorophom), characterized in that said isomer is obtained by isomerizing a second geometric isozyme to which the olefin proton appears in the weakest magnetic field of the PMR spectrum (deiterohlorofor) by irradiation with rays.

A process for obtaining one of the two geometric isomers of a triazole compound having the formula:

Where Rg, Rj and n are as defined in Clause I of the patent formula, wherein the olefin proton appears in the strongest magnetic field of the PMR spectrum (deiterohloroform), characterized by said isomer being obtained by isomerizing a mixture of geometric isomers of the wells by irradiation with rays. 10. A process for obtaining a deometric isomer, the formula of which is.

- 4 wherein Rj and n are as defined in claim I of claim 1, wherein said isomer is obtained by reduction of one of the geometric isomers of the triazole compound for mula irj - 4

R 2 wherein R 1, R j and n are as defined in claim 1 of the patent formula, wherein the olefin proton is present in the strongest magnetic field of the PMR spectrum (deuterochloroform). • II. Method of obtaining the geometric isomer, the formula of which is: ORj

wherein R 1 is C 1 -C 4 alkyl, C 1 -C 4 alkenyl or 2-propynyl, and R 1, R 4 and n are as defined in claim 1 of the patent formula, wherein said isomer is obtained by subjecting it to chemical exposure geometric isomer of formula OE

! VCH * C - CH - R, (H 5 > n N HI! -1 where and n is as defined in Clause I of the patent formula and obtained by reducing one of the two geometric isomers of the triazole compound having the formula: 5 LV 10023 Ο

wherein Ej and n are as defined in the patent formula I, wherein the olefin proton appears in the strongest magnetic field of the PMR spectrum (deuterochloroform), or its alcoholate with reactive C 1-6 alkyl, C 1-10 alkenyl or 2- propinyl derivative base, or salts thereof.

12. Fungicides, herbicides and / or agricultural and horticultural plant growth regulators, characterized in that they contain, as active ingredients, a geometric isomer of the formula n-GH < Vn 0RT I 1 = C-CH - RI II II -N Rj, Rp, Rj and n are as defined in Clause I of the patent formula, the war is obtained by reducing one of the geometric isomers of the triazole compound of formula I

^ TVgH = G - C - R, I / IK »1 u_N where R £» Rj and n are defined in Clause I of the patent formula, wherein the olefin proton appears in the strongest magnetic field of the FM8 spectrum (deuterochloroform) or subsequently etherifying the resulting reducing product or salts.